Photoreduction fuels biogeochemical cycling of iron in Spain's acid rivers

USGS Publications Warehouse

Gammons, C.H.; Nimick, D.A.; Parker, S.R.; Snyder, D.M.; McCleskey, R. Blaine; Amils, R.; Poulson, S.R.

2008-01-01

A number of investigations have shown that photoreduction of Fe(III) causes midday accumulations of dissolved Fe(II) in rivers and lakes, leading to large diel (24-h) fluctuations in the concentration and speciation of total dissolved iron. Less well appreciated is the importance of photoreduction in providing chemical energy for bacteria to thrive in low pH waters. Diel variations in water chemistry from the highly acidic (pH 2.3 to 3.1) Ri??o Tinto, Ri??o Odiel, and Ri??o Agrio of southwestern Spain (Iberian Pyrite Belt) resulted in daytime increases in Fe(II) concentration of 15 to 66????M at four diel sampling locations. Dissolved Fe(II) concentrations increased with solar radiation, and one of the stream sites showed an antithetic relationship between dissolved Fe(II) and Fe(III) concentrations; both results are consistent with photoreduction. The diel data were used to estimate rates of microbially catalyzed Fe(II) oxidation (1 to 3??nmol L- 1 s- 1) and maximum rates of Fe(III) photoreduction (1.7 to 4.3??nmol L- 1 s- 1). Bioenergetic calculations indicate that the latter rates are sufficient to build up a population of Fe-oxidizing bacteria to the levels observed in the Ri??o Tinto in about 30??days. We conclude that photoreduction plays an important role in the bioenergetics of the bacterial communities of these acidic rivers, which have previously been shown to be dominated by autotrophic Fe(II)-oxidizers such as Acidithiobacillus ferrooxidans and Leptospirillum ferrooxidans. Given the possibility of the previous existence of acidic, Fe(III)-rich water on Mars, photoreduction may be an important process on other planets, a fact that could have implications to astrobiological research. ?? 2008 Elsevier B.V. All rights reserved.

Colloid formation and metal transport through two mixing zones affected by acid mine drainage near Silverton, Colorado

USGS Publications Warehouse

Schemel, L.E.; Kimball, B.A.; Bencala, K.E.

2000-01-01

Stream discharges and concentrations of dissolved and colloidal metals (Al, Ca, Cu, Fe, Mg, Mn, Pb, and Zn), SO4, and dissolved silica were measured to identify chemical transformations and determine mass transports through two mixing zones in the Animas River that receive the inflows from Cement and Mineral Creeks. The creeks were the dominant sources of Al, Cu, Fe, and Pb, whereas the upstream Animas River supplied about half of the Zn. With the exception of Fe, which was present in dissolved and colloidal forms, the metals were dissolved in the acidic, high-SO4 waters of Cement Creek (pH 3.8). Mixing of Cement Creek with the Animas River increased pH to near-neutral values and transformed Al and some additional Fe into colloids which also contained Cu and Pb. Aluminium and Fe colloids had already formed in the mildly acidic conditions in Mineral Creek (pH 6.6) upstream of the confluence with the Animas River. Colloidal Fe continued to form downstream of both mixing zones. The Fe- and Al-rich colloids were important for transport of Cu, Pb, and Zn, which appeared to have sorbed to them. Partitioning of Zn between dissolved and colloidal phases was dependent on pH and colloid concentration. Mass balances showed conservative transports for Ca, Mg, Mn, SO4, and dissolved silica through the two mixing zones and small losses (< 10%) of colloidal Al, Fe and Zn from the water column.

Diel changes in metal concentrations in a geogenically acidic river: Rio Agrio, Argentina

NASA Astrophysics Data System (ADS)

Parker, Stephen R.; Gammons, Christopher H.; Pedrozo, Fernando L.; Wood, Scott A.

2008-12-01

Rio Agrio in Patagonia, Argentina is a geogenically acidic stream that derives its low-pH waters from condensation of acidic gases near its headwaters on the flanks of the active Copahue Volcano. This study reports the results of three diel (24-h) water samplings in three different pH regimes (3.2, 4.4 and 6.3) along the river. Changes in the concentration and speciation of Fe dominated the diel chemical changes at all three sites, although the timing and intensity of these cycles were different in each reach. At the two acidic sampling sites, total dissolved Fe and dissolved Fe(III) concentrations decreased during the day and increased at night, whereas dissolved Fe(II) showed the reverse pattern. These cycles are explained by Fe(III) photoreduction, as well as enhanced rates of precipitation of hydrous ferric oxide (HFO) during the warm afternoon hours. A strong correlation was observed between Fe(III) and As at the furthest upstream (pH 3.2) site, most likely due to co-precipitation of As with HFO. At the downstream (pH 6.3) location, Fe(II) concentrations increased at night, as did concentrations of rare earth elements and dissolved Al. Photoreduction does not appear to be an important process at pH 6.3, although it may be indirectly responsible for the observed diel cycle of Fe(II) due to advection of photochemically produced Fe(II) from acidic upstream waters. The results of this study of a naturally-acidic river are very similar to diel trends recently obtained from mining-impacted streams receiving acid rock drainage. The results are also used to explore the link between geochemistry and microbiology in acidic eco-systems. For example, Fe(III) photoreduction produces chemical potential energy (in the form of metastable Fe 2+) that helps support the bacterial community in this unique extreme environment.

Glacial influence on the geochemistry of riverine iron fluxes to the Gulf of Alaska and effects of deglaciation

USGS Publications Warehouse

Schroth, A.W.; Crusius, John; Chever, F.; Bostick, B.C.; Rouxel, O.J.

2011-01-01

Riverine iron (Fe) derived from glacial weathering is a critical micronutrient source to ecosystems of the Gulf of Alaska (GoA). Here we demonstrate that the source and chemical nature of riverine Fe input to the GoA could change dramatically due to the widespread watershed deglaciation that is underway. We examine Fe size partitioning, speciation, and isotopic composition in tributaries of the Copper River which exemplify a long-term GoA watershed evolution from one strongly influenced by glacial weathering to a boreal-forested watershed. Iron fluxes from glacierized tributaries bear high suspended sediment and colloidal Fe loads of mixed valence silicate species, with low concentrations of dissolved Fe and dissolved organic carbon (DOC). Iron isotopic composition is indicative of mechanical weathering as the Fe source. Conversely, Fe fluxes from boreal-forested systems have higher dissolved Fe concentrations corresponding to higher DOC concentrations. Iron colloids and suspended sediment consist of Fe (hydr)oxides and organic complexes. These watersheds have an iron isotopic composition indicative of an internal chemical processing source. We predict that as the GoA watershed evolves due to deglaciation, so will the source, flux, and chemical nature of riverine Fe loads, which could have significant ramifications for Alaskan marine and freshwater ecosystems.

An empirical method for estimating instream pre-mining pH and dissolved Cu concentration in catchments with acidic drainage and ferricrete

USGS Publications Warehouse

Nimick, D.A.; Gurrieri, J.T.; Furniss, G.

2009-01-01

Methods for assessing natural background water quality of streams affected by historical mining are vigorously debated. An empirical method is proposed in which stream-specific estimation equations are generated from relationships between either pH or dissolved Cu concentration in stream water and the Fe/Cu concentration ratio in Fe-precipitates presently forming in the stream. The equations and Fe/Cu ratios for pre-mining deposits of alluvial ferricrete then were used to reconstruct estimated pre-mining longitudinal profiles for pH and dissolved Cu in three acidic streams in Montana, USA. Primary assumptions underlying the proposed method are that alluvial ferricretes and modern Fe-precipitates share a common origin, that the Cu content of Fe-precipitates remains constant during and after conversion to ferricrete, and that geochemical factors other than pH and dissolved Cu concentration play a lesser role in determining Fe/Cu ratios in Fe-precipitates. The method was evaluated by applying it in a fourth, naturally acidic stream unaffected by mining, where estimated pre-mining pH and Cu concentrations were similar to present-day values, and by demonstrating that inflows, particularly from unmined areas, had consistent effects on both the pre-mining and measured profiles of pH and Cu concentration. Using this method, it was estimated that mining has affected about 480 m of Daisy Creek, 1.8 km of Fisher Creek, and at least 1 km of Swift Gulch. Mean values of pH decreased by about 0.6 pH units to about 3.2 in Daisy Creek and by 1-1.5 pH units to about 3.5 in Fisher Creek. In Swift Gulch, mining appears to have decreased pH from about 5.5 to as low as 3.6. Dissolved Cu concentrations increased due to mining almost 40% in Daisy Creek to a mean of 11.7 mg/L and as much as 230% in Fisher Creek to 0.690 mg/L. Uncertainty in the fate of Cu during the conversion of Fe-precipitates to ferricrete translates to potential errors in pre-mining estimates of as much as 0.25 units for pH and 22% for dissolved Cu concentration. The method warrants further testing in other mined and unmined watersheds. Comparison of pre-mining water-quality estimates derived from the ferricrete and other methods in single watersheds would be particularly valuable. The method has potential for use in monitoring remedial efforts at mine sites with ferricrete deposits. A reasonable remediation objective might be realized when the downstream pattern of Fe/Cu ratios in modern streambed Fe-precipitates corresponds to the pattern in pre-mining alluvial ferricrete deposits along a stream valley.

Suspended particulate matter determines physical speciation of Fe, Mn, and trace metals in surface waters of Loire watershed.

PubMed

Baalousha, Mohamed; Stoll, Serge; Motelica-Heino, Mikaël; Guigues, Nathalie; Braibant, Gilles; Huneau, Frédéric; Le Coustumer, Philippe

2018-02-10

This study investigates the spatiotemporal variability of major and trace elements, dissolved organic carbon (DOC), total dissolved solids (TDS), and suspended particulate matter (SPM) in surface waters of several hydrosystems of the Loire River watershed in France. In particular, this study aims to delineate the impact of the abovementioned water physicochemical parameters on natural iron and manganese physical speciation (homoaggregation/heteroaggregation) among fine colloidal and dissolved (< 10 nm), colloidal (10-450 nm) and particulate (> 450 nm) phases in Loire River watershed. Results show that the chemistry of the Loire River watershed is controlled by two end members: magmatic and metamorphic petrographic context on the upper part of the watershed; and sedimentary rocks for the middle and low part of the Loire. The percentage of particulate Fe and Mn increased downstream concurrent with the increase in SPM and major cations concentration, whereas the percentage of colloidal Fe and Mn decreased downstream. Transmission electron microscopy analyses of the colloidal and particulate fractions (from the non-filtered water sample) revealed that heteroaggregation of Fe and Mn rich natural nanoparticles and natural organic matter to the particulate phase is the dominant mechanism. The heteroaggregation controls the partitioning of Fe and Mn in the different fractions, potentially due to the increase in the ionic strength, and divalent cations concentration downstream, and SPM concentration. These findings imply that SPM concentration plays an important role in controlling the fate and behavior of Fe and Mn in various sized fractions. Graphical abstract Physical speciation by heteroaggregation of (Fe-Mn) compounds: high [SPM] → [Fe-Mn] particulate faction; low {SPM] → [Fe-Mn] colloid-dissolved fraction.

Influence of sea level rise on iron diagenesis in an east Florida subterranean estuary

USGS Publications Warehouse

Roy, M.; Martin, J.B.; Cherrier, J.; Cable, J.E.; Smith, C.G.

2010-01-01

Subterranean estuary occupies the transition zone between hypoxic fresh groundwater and oxic seawater, and between terrestrial and marine sediment deposits. Consequently, we hypothesize, in a subterranean estuary, biogeochemical reactions of Fe respond to submarine groundwater discharge (SGD) and sea level rise. Porewater and sediment samples were collected across a 30-m wide freshwater discharge zone of the Indian River Lagoon (Florida, USA) subterranean estuary, and at a site 250. m offshore. Porewater Fe concentrations range from 0.5 ??M at the shoreline and 250. m offshore to about 286 ??M at the freshwater-saltwater boundary. Sediment sulfur and porewater sulfide maxima occur in near-surface OC-rich black sediments of marine origin, and dissolved Fe maxima occur in underlying OC-poor orange sediments of terrestrial origin. Freshwater SGD flow rates decrease offshore from around 1 to 0.1. cm/day, while bioirrigation exchange deepens with distance from about 10. cm at the shoreline to about 40. cm at the freshwater-saltwater boundary. DOC concentrations increase from around 75 ??M at the shoreline to as much as 700 ??M at the freshwater-saltwater boundary as a result of labile marine carbon inputs from marine SGD. This labile DOC reduces Fe-oxides, which in conjunction with slow discharge of SGD at the boundary, allows dissolved Fe to accumulate. Upward advection of fresh SGD carries dissolved Fe from the Fe-oxide reduction zone to the sulfate reduction zone, where dissolved Fe precipitates as Fe-sulfides. Saturation models of Fe-sulfides indicate some fractions of these Fe-sulfides get dissolved near the sediment-water interface, where bioirrigation exchanges oxic surface water. The estimated dissolved Fe flux is approximately 0.84 ??M Fe/day per meter of shoreline to lagoon surface waters. Accelerated sea level rise predictions are thus likely to increase the Fe flux to surface waters and local primary productivity, particularly along coastlines where groundwater discharges through sediments. ?? 2010 Elsevier Ltd.

Reactive Iron Delivery to the Central Gulf of Alaska via Two Mesoscale Eddies (Invited)

NASA Astrophysics Data System (ADS)

Lippiatt, S. M.; Brown, M. T.; Lohan, M. C.; Bruland, K. W.

2010-12-01

Coastal waters in the northern Gulf of Alaska (GoA) are considered Fe-rich and nitrate-poor, in contrast to the Fe-poor, high-nitrate, low chlorophyll (HNLC) waters of the central GoA. Mixing between these two regimes can lead to enhanced primary productivity. Mesoscale anticyclonic eddies are an important mechanism for cross-shelf exchange of coastal and HNLC waters. This presentation will discuss findings from a cruise in the GoA during late summer 2007, namely dissolved Fe, leachable particulate Fe (defined as the portion of the particulate Fe that is solubilized with a two hour, 25% acetic acid leach with a short heating step and a reducing agent), and nitrate. Leachable particulate Fe concentrations in coastal surface waters between Yakutat, AK and the Kenai Peninsula ranged from over 1 uM in the Alsek River plume to less than 5 nM at the base of Cook Inlet, and were more variable and at least an order of magnitude higher than dissolved Fe concentrations. Relatively low and consistent dissolved Fe (~2 nM) suggests that the system’s ability to solubilize this large concentration of leachable particulate Fe is overwhelmed by the massive input of glacial-derived particulate Fe. Suspended leachable particulate Fe is available for exchange to the dissolved phase and is suggested to maintain a relatively constant 2 nM concentration of dissolved Fe in the coastal GoA. Glacial meltwaters were not a significant source of nitrate compared to central GoA HNLC or upwelled waters. The work completed in the coastal GoA set the stage for assessing the delivery of this glacial-derived coastal Fe to HNLC waters via mesoscale eddies. Two mesoscale eddies were sampled during this study: a Sitka eddy located off Yakutat, Alaska and a Kenai eddy sampled off the shelf break near Kodiak Island. The temperature and salinity structures of the eddies reflected their coastal origin; core waters were warmer and fresher than surrounding basin waters, coincident with elevated dissolved and leachable particulate Fe. In the core of the Yakutat eddy at 50 - 100 m depth there was on average 0.8 nM reactive Fe (dissolved + leachable particulate Fe), approximately five times more reactive Fe compared to adjacent GoA basin waters (0.16 nM). At the same depths in the core of the Kenai eddy there was on average 1.9 nM reactive Fe, ten times more reactive Fe than the basin waters (0.19 nM). In addition, for a given density, core waters had elevated nitrate and silicate compared to outside the eddy. Storms can mix Fe-enriched eddy core waters to the surface. Furthermore, anticyclonic GoA eddies can be a significant source of Fe to HNLC waters when they propagate into the central GoA and eventually relax with the Fe and nutrient rich subsurface waters rebounding or upwelling towards the surface. The transport of coastal waters into central GoA waters via mesoscale eddies is shown to be an important mechanism for Fe delivery into this HNLC region.

Trace element distributions in the water column near the Deepwater Horizon well blowout.

PubMed

Joung, DongJoo; Shiller, Alan M

2013-03-05

To understand the impact of the Deepwater Horizon well blowout on dissolved trace element concentrations, samples were collected from areas around the oil rig explosion site during four cruises in early and late May 2010, October 2010, and October 2011. In surface waters, Ba, Fe, Cu, Ni, Mn, and Co were relatively well correlated with salinity during all cruises, suggesting mixing with river water was the main influence on metal distributions in these waters. However, in deep oil/gas plumes (1000-1400 m depth), modestly elevated concentrations of Co and Ba were observed in late May, compared with postblowout conditions. Analysis of the oil itself along with leaching experiments confirm the oil as the source of the Co, whereas increased Ba was likely due to drilling mud used in the top kill attempt. Deep plume dissolved Mn largely reflected natural benthic input, though some samples showed slight elevation probably associated with the top kill. Dissolved Fe concentrations were low and also appeared largely topographically controlled and reflective of benthic input. Estimates suggest that microbial Fe demand may have affected the Fe distribution but probably not to the extent of Fe becoming a growth-limiting factor. Experiments showed that the dispersant can have some limited impact on dissolved-particulate metal partitioning.

Evaluation of air sparging and vadose zone aeration for remediation of iron and manganese-impacted groundwater at a closed municipal landfill.

PubMed

Pleasant, Saraya; O'Donnell, Amanda; Powell, Jon; Jain, Pradeep; Townsend, Timothy

2014-07-01

High concentrations of iron (Fe(II)) and manganese (Mn(II)) reductively dissolved from soil minerals have been detected in groundwater monitoring wells near many municipal solid waste landfills. Air sparging and vadose zone aeration (VZA) were evaluated as remedial approaches at a closed, unlined municipal solid waste landfill in Florida, USA. The goal of aeration was to oxidize Fe and Mn to their respective immobile forms. VZA and shallow air sparging using a partially submerged well screen were employed with limited success (Phase 1); decreases in dissolved iron were observed in three of nine monitoring wells during shallow air sparging and in two of 17 wells at VZA locations. During Phase 2, where deeper air sparging was employed, dissolved iron levels decreased in a significantly greater number of monitoring wells surrounding injection points, however no radial pattern was observed. Additionally, in wells affected positively by air sparging (mean total iron (FeTOT) <4.2mg/L, after commencement of air sparging), rising manganese concentrations were observed, indicating that the redox potential of the groundwater moved from an iron-reducing to a manganese-reducing environment. The mean FeTOT concentration observed in affected monitoring wells throughout the study was 1.40 mg/L compared to a background of 15.38 mg/L, while the mean Mn concentration was 0.60 mg/L compared to a background level of 0.27 mg/L. Reference wells located beyond the influence of air sparging areas showed little variation in FeTOT and Mn, indicating the observed effects were the result of air injection activities at study locations and not a natural phenomenon. Air sparging was found effective in intercepting plumes of dissolved Fe surrounding municipal landfills, but the effect on dissolved Mn was contrary to the desired outcome of decreased Mn groundwater concentrations. Copyright © 2014 Elsevier B.V. All rights reserved.

Distinct Siderophores Contribute to Iron Cycling in the Mesopelagic at Station ALOHA

DOE Office of Scientific and Technical Information (OSTI.GOV)

Bundy, Randelle M.; Boiteau, Rene M.; McLean, Craig

The distribution of dissolved iron (Fe), total organic Fe-binding ligands, and siderophores were measured between the surface and 400 m at Station ALOHA, a long term ecological study site in the North Pacific Subtropical Gyre. Dissolved Fe concentrations were low throughout the water column and strong organic Fe-binding ligands exceeded dissolved Fe at all depths; varying from 0.9 nmol L -1 in the surface to 1.6 nmol L -1 below 150 m. Although Fe does not appear to limit microbial production, we nevertheless found siderophores at nearly all depths, indicating some populations of microbes were responding to Fe stress. Ferrioxaminemore » siderophores were most abundant in the upper water column, with concentrations between 0.1-2 pmol L -1, while a suite of amphibactins were found below 200 m with concentrations between 0.8-11 pmol L -1. The distinct vertical distribution of ferrioxamines and amphibactins may indicate disparate strategies for acquiring Fe from dust in the upper water column and recycled organic matter in the lower water column. Amphibactins were found to have conditional stability constants (log ) ranging from 12.0-12.5, while ferrioxamines had much stronger conditional stability constants ranging from 14.0-14.4, within the range of observed L1 ligands by voltammetry. We used our data to calculate equilibrium Fe speciation at Station ALOHA to compare the relative concentration of inorganic and siderophore complexed Fe. The results indicate that the concentration of Fe bound to siderophores was up to two orders of magnitude higher than inorganic Fe, suggesting that even if less bioavailable, siderophores were nevertheless a viable pathway for Fe acquisition by microbes at our study site. Finally, we observed rapid production of ferrioxamine E by particle-associated bacteria during incubation of freshly collected sinking organic matter. Fe-limitation may therefore be a factor in regulating carbon metabolism and nutrient regeneration in the mesopelagic.« less

Distinct Siderophores Contribute to Iron Cycling in the Mesopelagic at Station ALOHA

DOE PAGES

Bundy, Randelle M.; Boiteau, Rene M.; McLean, Craig; ...

2018-03-01

The distribution of dissolved iron (Fe), total organic Fe-binding ligands, and siderophores were measured between the surface and 400 m at Station ALOHA, a long term ecological study site in the North Pacific Subtropical Gyre. Dissolved Fe concentrations were low throughout the water column and strong organic Fe-binding ligands exceeded dissolved Fe at all depths; varying from 0.9 nmol L -1 in the surface to 1.6 nmol L -1 below 150 m. Although Fe does not appear to limit microbial production, we nevertheless found siderophores at nearly all depths, indicating some populations of microbes were responding to Fe stress. Ferrioxaminemore » siderophores were most abundant in the upper water column, with concentrations between 0.1-2 pmol L -1, while a suite of amphibactins were found below 200 m with concentrations between 0.8-11 pmol L -1. The distinct vertical distribution of ferrioxamines and amphibactins may indicate disparate strategies for acquiring Fe from dust in the upper water column and recycled organic matter in the lower water column. Amphibactins were found to have conditional stability constants (log ) ranging from 12.0-12.5, while ferrioxamines had much stronger conditional stability constants ranging from 14.0-14.4, within the range of observed L1 ligands by voltammetry. We used our data to calculate equilibrium Fe speciation at Station ALOHA to compare the relative concentration of inorganic and siderophore complexed Fe. The results indicate that the concentration of Fe bound to siderophores was up to two orders of magnitude higher than inorganic Fe, suggesting that even if less bioavailable, siderophores were nevertheless a viable pathway for Fe acquisition by microbes at our study site. Finally, we observed rapid production of ferrioxamine E by particle-associated bacteria during incubation of freshly collected sinking organic matter. Fe-limitation may therefore be a factor in regulating carbon metabolism and nutrient regeneration in the mesopelagic.« less

Iron in the aquifer system of Suffolk County, New York, 1990–98

USGS Publications Warehouse

Brown, Craig J.; Walter, Donald A.; Colabufo, Steven

1999-01-01

High concentrations of dissolved iron in ground water contribute to the biofouling of public-supply wells, and the treatment and remediation of biofouling are costly. Water companies on Long Island, N.Y., spend several million dollars annually to recondition, redevelop, and replace supply wells and distribution lines; treat dissolved iron with sequestering agents or by filtration; and respond to iron-related complaints by customers. This report summarizes the results of studies done by the U.S. Geological Survey, in cooperation with the Suffolk County Water Authority, to characterize the geochemistry and microbiology of iron in the aquifer system of Suffolk County. This information should be helpful for the siting and operation of supply wells.Concentrations of dissolved iron in Long Island's ground water, and the frequency of iron biofouling of wells, are highest in ground-water-discharge zones, particularly near the south shore. Ground water along a deep north-south flowpath of the Magothy aquifer in southwestern Suffolk County becomes anaerobic (oxygen deficient) and Fe(III) reducing at a distance of 8 to 10 kilometers south of the ground-water divide, and this change coincides with the downgradient increase in dissolved iron concentrations. The distribution of organic carbon, and the distribution and local variations in reactivity of Fe(III), in Magothy aquifer sediments have resulted in localized differences in redox microenvironments. For example, Fe(III)-reducing zones are associated with anaerobic conditions, where relatively large amounts of Fe(III) oxyhydroxide grain coatings are present, whereas sulfate-reducing zones are associated with lignite-rich lenses of silt and clay and appear to have developed in response to the depletion of available Fe(III) oxyhydroxides. The sulfate-reducing zones are characterized by relatively low concentrations of dissolved iron (resulting from iron-disulfide precipitation) and may be large enough to warrant water-supply development.Specific-capacity and water-quality data from wells screened in the Magothy aquifer indicate that water from biofouled wells contains higher median concentrations of total and dissolved iron and manganese, total phosphate, and dissolved sulfate, and lower median concentrations of dissolved oxygen and alkalinity, and lower pH, than does water from unaffected wells. Corresponding data from wells screened in the upper glacial aquifer indicate that water from biofouled wells contains higher median concentrations of total and dissolved manganese and dissolved sulfate, and lower pH, than does water from unaffected wells.Filamentous bacteria were detected in 31 (or 72 percent) of the 43 biofilm samples obtained from biofouled wells during reconditioning. The predominant filamentous organism was Gallionella ferruginea, a major biofouling agent in the upper glacial and Magothy aquifers throughout Suffolk County. Mineral-saturation indices indicate that most of the well-encrusting material is deposited when the wells are shut down. Furthermore, the use of treated water (which has a high pH and sometimes high concentrations of dissolved iron) for pump prelubrication when wells are shut down could greatly increase the rate of iron oxidation.

Evaluation of Fe(II) oxidation at an acid mine drainage site using laboratory-scale reactors

NASA Astrophysics Data System (ADS)

Brown, Juliana; Burgos, William

2010-05-01

Acid mine drainage (AMD) is a severe environmental threat to the Appalachian region of the Eastern United States. The Susquehanna and Potomac River basins of Pennsylvania drain to the Chesapeake Bay, which is heavily polluted by acidity and metals from AMD. This study attempted to unravel the complex relationships between AMD geochemistry, microbial communities, hydrodynamic conditions, and the mineral precipitates for low-pH Fe mounds formed downstream of deep mine discharges, such as Lower Red Eyes in Somerset County, PA, USA. This site is contaminated with high concentrations of Fe (550 mg/L), Mn (115 mg/L), and other trace metals. At the site 95% of dissolved Fe(II) and 56% of total dissolved Fe is removed without treatment, across the mound, but there is no change in the concentration of trace metals. Fe(III) oxides were collected across the Red Eyes Fe mound and precipitates were analyzed by X-ray diffraction, electron microscopy and elemental analysis. Schwertmannite was the dominant mineral phase with traces of goethite. The precipitates also contained minor amounts of Al2O3, MgO,and P2O5. Laboratory flow-through reactors were constructed to quantify Fe(II) oxidation and Fe removal over time at terrace and pool depositional facies. Conditions such as residence time, number of reactors in sequence and water column height were varied to determine optimal conditions for Fe removal. Reactors with sediments collected from an upstream terrace oxidized more than 50% of dissolved Fe(II) at a ten hour residence time, while upstream pool sediments only oxidized 40% of dissolved Fe(II). Downstream terrace and pool sediments were only capable of oxidizing 25% and 20% of Fe(II), respectively. Fe(II) oxidation rates measured in the reactors were determined to be between 3.99 x 10-8and 1.94 x 10-7mol L-1s-1. The sediments were not as efficient for total dissolved Fe removal and only 25% was removed under optimal conditions. The removal efficiency for all sediments decreased as residence time decreased and as water column depth increased. Control reactors with Co-60 irradiated sediments showed an increase in Fe concentration as a result of dissolution of the sediments; thus, it was concluded that Fe(II) oxidation in the reactors was a result of biological processes and not abiotic oxidation. It was also concluded that Fe(II) oxidation and removal rates were dependent upon geochemical gradients (pH, Fe(II) concentration) rather than depositional facies. Fluorescent in situ hybridization was also performed on field and reactor samples to determine which microbial communities were responsible for the highest Fe(II) oxidation rates.

Iron isotope constraints on arsenic release from Mekong Delta sediments, Cambodia

NASA Astrophysics Data System (ADS)

Matsumoto, T.; Yamaguchi, K. E.; Hirata, T.; Yamagata, Y.; Yamaguchi, A.; Abe, G.

2017-12-01

Arsenic-contaminated groundwater is a world-wide environmental problem and threatens more than 100 million people living in delta areas of South, SE and East Asia. It is typically associated with reducing aquifers with organic-rich alluvial sediments, little thermal gradients, low sulfate concentrations, and slow flushing rates. Such conditions are typical for low-lying countries in Asian deltas; however, compared to Bangladesh, Cambodia has received far less attention. Upon reductive dissolution of Fe-(oxyhydr)oxides that adsorbed As, Fe and As are released into solution as dissolved Fe2+ and arsenate, respectively. Following the oxidation of dissolved Fe2+, newly-formed Fe-(oxyhydr)oxides adsorb As again. Thus, in anoxic waters, concentrations of As correlate with those of dissolved Fe2+. Fluctuating redox conditions in the aquifer are control As release, although inhibition of adsorption of arsenate and arsenite onto the Fe-(oxyhydr)oxides occurs when the concentrations of phosphate, bicarbonate, silicate, and/or organic matter become sufficiently high. Biogeochemical redox reactions of Fe result in significant isotope fractionation (e.g., Johnson et al., 2008). We hypothesized that magnitude of isotope fractionation of Fe in the aquifer sediments, reflecting repeated (incomplete) redox reactions of Fe, may be proportional to the amount of total As release. We aim to calibrate the As release from aquifer sediment by Fe isotope analysis. As a preliminary study, series of sediment samples were collected from the Mekong Delta, Cambodia, in September 2016. Based on measurements by XRF, ICP-AES and ICP-MS, concentrations of As varied significantly covering the range from 4.5 to 15.5 µg/g with a median value of 11 µg/g (higher than the average crustal value of 5 µg/g), and those of Fe is from 2.6 to 9.7 wt.% with a median value of 7.1 wt.%. Concentrations of As and Fe show positive correlation (R2 = 0.72), indicating an effective redox cycling of Fe and As as stated above. Sediment incubation experiment to explore various pathways of As release would show time-series correlated changes in the Fe isotope compositions and As concentrations. The data obtained here are essential in investigating the mechanism of As release.

Iron oxidation kinetics and phosphorus immobilization at the groundwater-surface water interface

NASA Astrophysics Data System (ADS)

van der Grift, Bas; Rozemeijer, Joachim; Griffioen, Jasper; van der Velde, Ype

2014-05-01

Eutrophication of freshwater environments following diffuse nutrient loads is a widely recognized water quality problem in catchments. Fluxes of non-point P sources to surface waters originate from surface runoff and flow from soil water and groundwater into surface water. The availability of P in surface waters is controlled strongly by biogeochemical nutrient cycling processes at the soil-water interface. The mechanisms and rates of the iron oxidation process with associated binding of phosphate during exfiltration of anaerobic Fe(II) bearing groundwater are among the key unknowns in P retention processes in surface waters in delta areas where the shallow groundwater is typically pH-neutral to slightly acid, anoxic, iron-rich. We developed an experimental field set-up to study the dynamics in Fe(II) oxidation and mechanisms of P immobilization at the groundwater-surface water interface in an agricultural experimental catchment of a small lowland river. We physically separated tube drain effluent from groundwater discharge before it entered a ditch in an agricultural field. The exfiltrating groundwater was captured in in-stream reservoirs constructed in the ditch. Through continuous discharge measurements and weekly water quality sampling of groundwater, tube drain water, exfiltrated groundwater, and ditch water, we quantified Fe(II) oxidation kinetics and P immobilization processes across the seasons. This study showed that seasonal changes in climatic conditions affect the Fe(II) oxidation process. In winter time the dissolved iron concentrations in the in-stream reservoirs reached the levels of the anaerobic groundwater. In summer time, the dissolved iron concentrations of the water in the reservoirs are low, indicating that dissolved Fe(II) is completely oxidized prior to inflow into the reservoirs. Higher discharges, lower temperatures and lower pH of the exfiltrated groundwater in winter compared to summer shifts the location of the redox transition zone, with Fe(II) oxidation taking place in the soil surrounding the ditch during summer and in the surface water during winter. The dynamics in Fe(II) oxidation did not affect the dissolved P concentrations. The dissolved P concentrations of the in-stream reservoirs water were an order of magnitude lower than observed in the groundwater and have no seasonal trend. Our data showed preferential binding of P during initial stage of the Fe(II) oxidation process, indicating the formation of Fe(III)-phosphate precipitates. The formation of Fe(III)-phosphates at the groundwater-surface water interface is an important geochemical mechanism in the transformation of dissolved phosphate to particulate phosphate and therefore a major control on the P retention in natural waters that drain anaerobic aquifers.

The 3D Distribution of Dissolved and Colloidal Fe, Mn, Zn, Cu, Ni, Cd and Pb in the Western Antarctic Peninsula Shelf Region; Implications for Natural Fe Fertilization

NASA Astrophysics Data System (ADS)

Sherrell, R. M.; Fitzsimmons, J. N.; Roccanova, J.; Schofield, O.; Meredith, M. P.

2016-02-01

The Western Antarctic Peninsula (WAP) shelf region is is a natural Fe fertilization zone where primary production exceeds that of the adjacent open Southern Ocean. Until recently, however, distributions of Fe and of other bioactive metals were completely lacking for the WAP, and the sources and delivery mechanisms of Fe to the euphotic zone were only speculated upon. We have previously presented surface water (2m) dissolved (dTM, <0.2µm) and particulate (pTM, >0.45µm) distributions for Fe and a suite of other bioactive metals over the WAP shelf, covering the Palmer LTER sampling grid for Jan. 2010, 2011 and 2012. We now report the first complete 3D distribution of dissolved and colloidal Fe (and Mn, Zn, Cu, Ni, Cd and Pb) over the LTER grid in Jan. 2015, allowing assessment of dFe size speciation, sources and transport pathways in this dynamic shelf system. Dissolved metals were analyzed by automated offline preconcentration (seaFAST-pico, ESI) followed by sector-field ICP-MS. We confirm previous findings of low ( 0.1nM) dFe in surface waters on the mid-outer shelf in the northern portion of the grid, and now find that concentrations at this level or below persist through the euphotic zone. However, dFe increases rapidly with depth, with low surface values underlain by substantially higher concentrations even at 50m. Inner shelf surface waters are generally substantially > 0.1nM, suggesting Fe replete conditions in this region. Vertical profiles reveal that dFe generally increases with depth, much moreso in the inner shelf (dFe up to 5.0nM) than the outer shelf. A general N-S gradient in dFe is also evident, with concentrations higher in the southern WAP, especially in Marguerite Bay. In addition, shelf stations often show a dFe maximum suggesting remineralization from sinking biogenic particles. These findings for dFe and for the other metals, will be used to help unravel the biogeochemical workings of natural Fe fertilization in this region.

Effects of dissolved oxygen on dye removal by zero-valent iron.

PubMed

Wang, Kai-Sung; Lin, Chiou-Liang; Wei, Ming-Chi; Liang, Hsiu-Hao; Li, Heng-Ching; Chang, Chih-Hua; Fang, Yung-Tai; Chang, Shih-Hsien

2010-10-15

Effects of dissolved oxygen concentrations on dye removal by zero-valent iron (Fe(0)) were investigated. The Vibrio fischeri light inhibition test was employed to evaluate toxicity of decolorized solution. Three dyes, Acid Orange 7 (AO7, monoazo), Reactive Red 120 (RR120, diazo), and Acid Blue 9 (AB9, triphenylmethane), were selected as model dyes. The dye concentration and Fe(0) dose used were 100 mg L(-1) and 30 g L(-1), respectively. Under anoxic condition, the order for dye decolorization was AO7>RR120>AB9. An increase in the dissolved oxygen concentrations enhanced decolorization and chemical oxygen demand (COD) removal of the three dyes. An increase in gas flow rates also improved dye and COD removals by Fe(0). At dissolved oxygen of 6 mg L(-1), more than 99% of each dye was decolorized within 12 min and high COD removals were obtained (97% for AO7, 87% for RR120, and 93% for AB9). The toxicity of decolorized dye solutions was low (I(5)<40%). An increase in DO concentrations obviously reduced the toxicity. When DO above 2 mg L(-1) was applied, low iron ion concentration (13.6 mg L(-1)) was obtained in the decolorized AO7 solution. 2010 Elsevier B.V. All rights reserved.

Combined effects of hydrographic structure and iron and copper availability on the phytoplankton growth in Terra Nova Bay Polynya (Ross Sea, Antarctica)

NASA Astrophysics Data System (ADS)

Rivaro, Paola; Luisa Abelmoschi, Maria; Grotti, Marco; Ianni, Carmela; Magi, Emanuele; Margiotta, Francesca; Massolo, Serena; Saggiomo, Vincenzo

2012-04-01

Surface water (<100 m) samples were collected from the Terra Nova Bay polynya region of the Ross Sea (Antarctica) in January 2006, with the aim of evaluating the individual and combined effects of hydrographic structure, iron and copper concentration and availability on the phytoplankton growth. The measurements were conducted within the framework of the Climatic Long Term Interaction for the Mass-balance in Antarctica (CLIMA) Project of the Programma Nazionale di Ricerca in Antartide activities. Dissolved oxygen, nutrients, phytoplankton pigments and concentration and complexation of dissolved trace metals were determined. Experimental data were elaborated by Principal Component Analysis (PCA). As a result of solar heating and freshwater inputs from melting sea-ice, the water column was strongly stratified with an Upper Mixed Layer 4-16 m deep. The integrated Chl a in the layer 0-100 m ranged from 60 mg m-2 to 235 mg m-2, with a mean value of 138 mg m-2. The pigment analysis showed that diatoms dominated the phytoplankton assemblage. Major nutrients were generally high, with the lowest concentration at the surface and they were never fully depleted. The Si:N drawdown ratio was close to the expected value of 1 for Fe-replete diatoms. We evaluated both the total and the labile dissolved fraction of Fe and Cu. The labile fraction was operationally defined by employing the chelating resin Chelex-100, which retains free and loosely bound trace metal species. The total dissolved Fe ranged from 0.48 to 3.02 nM, while the total dissolved Cu from 3.68 to 6.84 nM. The dissolved labile Fe ranged from below the detection limit (0.15 nM) to 1.22 nM, and the dissolved labile Cu from 0.31 to 1.59 nM, respectively. The labile fractions measured at 20 m were significantly lower than values in 40-100 m samples. As two stations were re-sampled 5 days later, we evaluated the short-term variability of the physical and biogeochemical properties. In particular, in a re-sampled station at 20 m, the total dissolved Fe increased and the total dissolved Cu decreased, while their labile fraction was relatively steady. As a result of the increase in total Fe, the percentage of the labile Fe decreased. An increase of the Si:N, Si:P and Si:FUCO ratios was measured also in the re-sampled station. On this basis, we speculated that a switch from a Fe-replete to a Fe-deplete condition was occurring.

Deconvolution of trace element (As, Cr, Mo, Th, U) sources and pathways to surface waters of a gold mining-influenced watershed.

PubMed

Grosbois, C; Schäfer, J; Bril, H; Blanc, G; Bossy, A

2009-03-01

The Upper Isle River (SW France) drains the second most productive gold-mining district of France. A high resolution survey during one hydrological year of As, Cl(-), Cr, Fe, Mn, Mo, SO(4)(2-), Th and U dissolved concentrations in surface water aimed to better understand pathways of trace element export to the river system downstream from the mining district. Dissolved concentrations of As (up to 35000 ng/L) and Mo (up to 292 ng/L) were about 3-fold higher than the regional dissolved background and showed a negative logarithmic relation with discharge. Dissolved concentrations of Cr (up to 483 ng/L), Th (up to 48 ng/L) and U (up to 184 ng/L) increased with discharge. Geochemical relationships between molar ratios in surface water, geochemical background as well as rain- and groundwater data were combined. The contrasting behavior of distinct element groups was explained by a scenario involving three seasonal components: (i) The high flow component is poorly concentrated in As and Mo but highly concentrated in Cr, Th, U. This has been attributed to diffuse sources such as water-soil interactions, atmospheric inputs, bedrock and bed sediment weathering. Although this component probably also includes a contribution by weathering of sulfide veins, this signal is masked by dilution. (ii) One low flow component presents high SO(4)(2-), Fe, As and Mo and moderate Cr, Th and U concentrations. This component has been attributed to point sources such as mine gallery effluents, mining waste weathering and groundwater inputs from natural and/or mining-induced sulfide oxidation in the ore deposit. (iii) A second low flow component showing high As plus Mo concentrations associated with very low SO(4)(2-), Fe, Cr, Th and U concentrations, probably reflects trace element scavenging by ferric oxyhydroxide formation in the adjacent aquifer. This is supported by the decrease of Fe, Cr, Th and U in surface waters. Flux estimates suggest contrasting element-specific impacts on annual dissolved fluxes. Runoff may account for the major part of annual dissolved As, Mo, Th and U fluxes in the Upper Isle River. Inputs related to sulfide oxidation respectively contributed approximately 30% and approximately 24% to annual As and Mo fluxes. The formation of ferric oxyhydroxides strongly retained Cr, Th and U during the low flow, limiting their dissolved concentrations in surface waters. If this process may eventually decrease As mobility, its impact on dissolved As concentrations in surface water may be limited or/and counterbalanced by As release during sulfide oxidation.

High Magnetic Susceptibility in a Highly Saline Sulfate-Rich Aquifer Undergoing Biodegradation of Hydrocarbon Results from Sulfate Reduction.

NASA Astrophysics Data System (ADS)

Atekwana, E. A.; Enright, A.; Ntarlagiannis, D.; Slater, L. D.; Bernier, R.; Beaver, C. L.; Rossbach, S.

2016-12-01

We investigated the chemical and stable carbon isotope composition of groundwater in a highly saline aquifer contaminated with hydrocarbon. Our aim to evaluate hydrocarbon degradation and to constrain the geochemical conditions that generated high anomalous magnetic susceptibility (MS) signatures observed at the water table interface. The occurrence of high MS in the water table fluctuating zone has been attributed to microbial iron reduction, suggesting the use of MS as a proxy for iron cycling. The highly saline aquifer had total dissolved solids concentrations of 3.7 to 29.3 g/L and sulfate concentrations of 787 to 37,100 mg/L. We compared our results for groundwater locations with high hydrocarbon contamination (total petroleum hydrocarbon (TPH) >10 mg/L), at lightly contaminated (TPH <10 mg/L) and locations with no contaminations. Our results for the terminal electron acceptors (TEAs) dissolved oxygen (DO), nitrate (NO3-), dissolved iron (Fe2+) , dissolved manganese (Mn2+), sulfate (SO42-) and methane (CH4) suggest a chemically heterogeneous aquifer, probably controlled by heterogeneous distribution of TEAs and contamination (type of hydrocarbon, phase and age of contamination). The concentrations of dissolved inorganic carbon (DIC) ranged from 67 to 648 mg C/L and the stable carbon isotope (δ13CDIC) ranged from -30.0‰ to 1.0 ‰ and DIC-δ13CDIC modeling indicates that the carbon in the DIC is derived primarily from hydrocarbon degradation. The concentrations of Fe2+ in the aquifer ranged from 0.1 to 55.8 mg/L, but was mostly low, averaging 2.7+10.9 mg/L. Given the low Fe2+ [AE1] in the aqueous phase and the high MS at contaminated locations, we suggest that the high MS observed does not arise from iron reduction but rather from sulfate reduction. Sulfate reduction produces H2S which reacts with Fe2+ to produce ferrous sulfide (Fe2+S) or the mixed valence greigite (Fe2+Fe3+2S4). We conclude that in highly saline aquifers with high concentrations of sulfate and contaminated with hydrocarbon, dominance of sulfate reduction as the TEA is responsible for iron cycling and therefore the high MS associated with biodegradation. [AE1]What about sulfate concentrations? And the range in salinity? You need to add these values to the bastrcat

Geochemical modeling of iron, sulfur, oxygen and carbon in a coastal plain aquifer

USGS Publications Warehouse

Brown, C.J.; Schoonen, M.A.A.; Candela, J.L.

2000-01-01

Fe(III) reduction in the Magothy aquifer of Long Island, NY, results in high dissolved-iron concentrations that degrade water quality. Geochemical modeling was used to constrain iron-related geochemical processes and redox zonation along a flow path. The observed increase in dissolved inorganic carbon is consistent with the oxidation of sedimentary organic matter coupled to the reduction of O2 and SO4/2- in the aerobic zone, and to the reduction of SO4/2- in the anaerobic zone; estimated rates of CO2 production through reduction of Fe(III) were relatively minor by comparison. The rates of CO2 production calculated from dissolved inorganic carbon mass transfer (2.55 x 10-4 to 48.6 x 10-4 mmol 1-1 yr-1) generally were comparable to the calculated rates of CO2 production by the combined reduction of O2, Fe(III) and SO4/2- (1.31 x 10-4 to 15 x 10-4 mmol 1-1 yr-1). The overall increase in SO4/2- concentrations along the flow path, together with the results of mass-balance calculations, and variations in ??34S values along the flow path indicate that SO4/2- loss through microbial reduction is exceeded by SO4/2- gain through diffusion from sediments and through the oxidation of FeS2. Geochemichal and microbial data on cores indicate that Fe(III) oxyhydroxide coatings on sediment grains in local, organic carbon- and SO4/2- -rich zones have localized SO4/2- -reducing zones in which the formation of iron disulfides been depleted by microbial reduction and resulted in decreases dissolved iron concentrations. These localized zones of SO4/2- reduction, which are important for assessing zones of low dissolved iron for water-supply development, could be overlooked by aquifer studies that rely only on groundwater data from well-water samples for geochemical modeling. (C) 2000 Elsevier Science B.V.Fe(III) reduction in the Magothy aquifer of Long Island, NY, results in high dissolved-iron concentrations that degrade water quality. Geochemical modeling was used to constrain iron-related geochemical processes and redox zonation along a flow path. The observed increase in dissolved inorganic carbon is consistent with the oxidation of sedimentary organic matter coupled to the reduction of O2 and SO42- in the aerobic zone, and to the reduction of SO42- in the anaerobic zone; estimated rates of CO2 production through reduction of Fe(III) were relatively minor by comparison. The rates of CO2 production calculated from dissolved inorganic carbon mass transfer (2.55??10-4 to 48.6??10-4mmol l-1yr-1) generally were comparable to the calculated rates of CO2 production by the combined reduction of O2, Fe(III) and SO42- (1.31??10-4 to 15??10-4mmol l-1yr-1). The overall increase in SO42- concentrations along the flow path, together with the results of mass-balance calculations, and variations in ??34S values along the flow path indicate that SO42- loss through microbial reduction is exceeded by SO42- gain through diffusion from sediments and through the oxidation of FeS2. Geochemical and microbial data on cores indicate that Fe(III) oxyhydroxide coatings on sediment grains in local, organic carbon- and SO42--rich zones have been depleted by microbial reduction and resulted in localized SO42--reducing zones in which the formation of iron disulfides decreases dissolved iron concentrations. These localized zones of SO42- reduction, which are important for assessing zones of low dissolved iron for water-supply development, could be overlooked by aquifer studies that rely only on groundwater data from well-water samples for geochemical modeling.

Dissolved and particulate 230Th-232Th in the Central Equatorial Pacific Ocean: Evidence for far-field transport of the East Pacific Rise hydrothermal plume

NASA Astrophysics Data System (ADS)

Lopez, Grecia I.; Marcantonio, Franco; Lyle, Mitch; Lynch-Stieglitz, Jean

2015-12-01

We assess the distribution of 230Th and 232Th along a latitudinal gradient in the Central Equatorial Pacific Ocean (∼155°W-159°W) at two sites: 8°N and the equator. The dissolved 230Th concentration profile at 8°N increases nearly linearly from the surface to 2000 m, exhibiting behavior consistent with thermodynamic reversible scavenging. However, from 2000 m to 3000 m, the dissolved 230Th concentrations exhibit little change, before increasing slightly from 3000 m to the bottom. At this site dissolved 230Th concentrations range from 1.1 fg/kg at 100 m to 55.2 fg/kg at 4600 m. At the equator, dissolved 230Th concentrations are slightly lower, and range from undetectable at 25 m to 19.1 fg/kg at 3038 m. The pattern in the dissolved 230Th concentration profile at the equator is indistinguishable from that at 8°N. The mid-depth-water deviation from equilibrium reversible scavenging between 2 and 3 km in the 230Th profiles (lower concentrations than expected) at both sites occurs in the interval of the water column that is consistent with an interval that has high concentrations of 3He and dissolved Fe at other nearby sites. This 3He- and Fe-rich signal has been traced to hydrothermal plumes from the East Pacific Rise, thousands of kilometers away. We hypothesize that the lower concentrations of 230Th in mid-depth waters of the Central Equatorial Pacific are a result of a 5000-km transit of waters that have had their 230Th scavenged by Fe-Mn particulates close to the EPR. Oceanic residence times of thorium combined with dissolved 232Th concentrations suggest dust fluxes of about ∼ 0.5- 0.6 gm-2yr-1 to the sea surface. These fluxes are in agreement with other empirical studies in the Pacific, but are higher than those suggested by global atmospheric circulation models.

Effect of Organic Substances on the Efficiency of Fe(Ii) to Fe(Iii) Oxidation and Removal of Iron Compounds from Groundwater in the Sedimentation Process

NASA Astrophysics Data System (ADS)

Krupińska, Izabela

2017-09-01

One of the problems with iron removal from groundwater is organic matter. The article presents the experiments involved groundwater samples with a high concentration of total iron - amounting to 7.20 mgFe/dm3 and an increased amount of organic substances (TOC from 5.50 to 7.50 mgC/dm3). The water samples examined differed in terms of the value of the ratio of the TOC concentration and the concentration of total iron (D). It was concluded that with increase in the coexistence ratio of organic substances and total iron in water (D = [TOC]/[Fetot]), efficiency of Fe(II) to Fe(III) oxidization with dissolved oxygen decreased, while the oxidation time was increasing. This rule was not demonstrated for potassium manganate (VII) when used as an oxidizing agent. The application of potassium manganate (VII) for oxidation of Fe(II) ions produced the better results in terms of total iron concentration reduction in the sedimentation process than the oxidation with dissolved oxygen.

Thorium distributions in high- and low-dust regions and the significance for iron supply

NASA Astrophysics Data System (ADS)

Hayes, Christopher T.; Rosen, Jeffrey; McGee, David; Boyle, Edward A.

2017-02-01

Thorium and uranium isotopes (232Th, 230Th, 238U, and 234U) were investigated to refine their use for estimating mineral dust deposition and Fe delivery to the ocean. U concentrations and isotope ratios were consistent with conservative behavior and can safely be described using published U-salinity relationships and global average seawater isotopic composition. Near Barbados, waters affected by the Amazon outflow contained elevated 232Th. This signals one region where the thorium-dust method is inaccurate because of a confounding continental input. Dissolved 232Th fluxes in this region suggest that Amazonian Fe supply to the adjacent open ocean is much larger than local atmospheric deposition. The colloidal content of dissolved Th south of Bermuda was found to be quite small (2-6%), similar to that found north of Hawaii, despite the order of magnitude higher dust deposition in the Atlantic. This finding supports the assumption that dissolved 232Th and 230Th are scavenged at the same rate despite their different sources and also sheds light on the increase of dissolved 232Th fluxes with integrated depth. Outside the region influenced by Amazon River waters, dissolved 232Th fluxes are compared with Bermudan aerosol Fe deposition to estimate that fractional Th solubility is around 20% in this region. Finally, new dissolved and soluble Fe, Mn, and Cr data from the subtropical North Pacific support the idea that Fe concentrations in the remote ocean are highly buffered, whereas 232Th has a larger dynamic range between high- and low-dust regions.

Trace Metals in Urban Stormwater Runoff and their Management

NASA Astrophysics Data System (ADS)

Li, T.; Hall, K.; Li, L. Y.; Schreier, H.

2009-04-01

In past decades, due to the rapid urbanization, land development has replaced forests, fields and meadows with impervious surfaces such as roofs, parking lots and roads, significantly affecting watershed quality and having an impact on aquatic systems. In this study, non-point source pollution from a diesel bus loop was assessed for the extent of trace metal contamination of Cu, Mn, Fe, and Zn in the storm water runoff. The study was carried out at the University of British Columbia (UBC) in the Greater Vancouver Regional District (GVRD) of British Columbia, Canada. Fifteen storm events were monitored at 3 sites from the diesel bus loop to determine spatial and temporal variations of dissolved and total metal concentrations in the storm water runoff. The dissolved metal concentrations were compared with the provincial government discharge criteria and the bus loop storm water quality was also compared with previous studies conducted across the GVRD urban area. To prevent storm water with hazardous levels of contaminants from being discharged into the urban drainage system, a storm water catch basin filter was installed and evaluated for its efficiency of contaminants removal. The perlite filter media adsorption capacities for the trace metals, oil and grease were studied for better maintenance of the catch basin filter. Dissolved copper exceeded the discharge criteria limit in 2 out of 15 cases, whereas dissolved zinc exceeded the criteria in 4 out of 15 cases, and dissolved manganese was below the criteria in all of the events sampled. Dissolved Cu and Zn accounted for 36 and 45% of the total concentration, whereas Mn and Fe only accounted for 20 and 4% of their total concentration, respectively. Since they are more mobile and have higher bioaccumulation potentials, Zn and Cu are considered to be more hazardous to the aquatic environment than Fe and Mn. With high imperviousness (100%) and intensive traffic at the UBC diesel bus loop, trace metal concentrations were 3, 0.7, 9, and 3.2 times higher than the GVRD urban area limits for Cu, Mn, Fe, and Zn, respectively. The filter showed high and stable capture efficiencies in total metals (Cu 62%, Mn 75%, Fe 83%, Zn 62%), dissolved metals (Cu 39%, Mn 37%, Fe 47%, Zn 32%), turbidity (72%), and suspended solids (74%) removal during the first month of operation. After that, there was gradual degradation. The catch basin filter performance improved significantly for the suspended solids and total metal removal after cleaning. However, the perlite filter medium showed poor performance for dissolved metal removal in the second study period. Based on the findings, a catch basin filter is effective in storm water management to control suspended solids loading from storm water runoff.

Enhanced Al and Zn removal from coal-mine drainage during rapid oxidation and precipitation of Fe oxides at near-neutral pH

USGS Publications Warehouse

Burrows, Jill E.; Cravotta, Charles A.; Peters, Stephen C.

2017-01-01

Net-alkaline, anoxic coal-mine drainage containing ∼20 mg/L FeII and ∼0.05 mg/L Al and Zn was subjected to parallel batch experiments: control, aeration (Aer 1 12.6 mL/s; Aer 2 16.8 mL/s; Aer 3 25.0 mL/s), and hydrogen peroxide (H2O2) to test the hypothesis that aeration increases pH, FeII oxidation, hydrous FeIII oxide (HFO) formation, and trace-metal removal through adsorption and coprecipitation with HFO. During 5.5-hr field experiments, pH increased from 6.4 to 6.7, 7.1, 7.6, and 8.1 for the control, Aer 1, Aer 2, and Aer 3, respectively, but decreased to 6.3 for the H2O2 treatment. Aeration accelerated removal of dissolved CO2, Fe, Al, and Zn. In Aer 3, dissolved Al was completely removed within 1 h, but increased to ∼20% of the initial concentration after 2.5 h when pH exceeded 7.5. H2O2 promoted rapid removal of all dissolved Fe and Al, and 13% of dissolved Zn.Kinetic modeling with PHREEQC simulated effects of aeration on pH, CO2, Fe, Zn, and Al. Aeration enhanced Zn adsorption by increasing pH and HFO formation while decreasing aqueous CO2 available to form ZnCO30 and Zn(CO3)22− at high pH. Al concentrations were inconsistent with solubility control by Al minerals or Al-containing HFO, but could be simulated by adsorption on HFO at pH < 7.5 and desorption at higher pH where Al(OH)4− was predominant. Thus, aeration or chemical oxidation with pH adjustment to ∼7.5 could be effective for treating high-Fe and moderate-Zn concentrations, whereas chemical oxidation without pH adjustment may be effective for treating high-Fe and moderate-Al concentrations.

Fe, Zn, and Cd stable isotopes from the eastern tropical South Pacific from GEOTRACES cruise GP16 - Methods and data

NASA Astrophysics Data System (ADS)

Helgoe, J. M.; Townsend, E.; John, S.

2014-12-01

A new method has been developed for the rapid analysis of metal concentrations and stable isotope ratios using a prepFAST automated sample processing robot. Although concentrations and isotopes are processed separately, similar methods are used for both. Initially all seawater is acidified to pH 2. Then Nobias resin with EDTA/IDA functional groups is added to either 10mL of sample for concentrations or ~1L samples for isotopes. Fe binds to the resin at low pH, and the pH is subsequently raised to allow Zn and Cd to bind. For concentration analyses, all subsequent chemistry is automated on the prepFAST including removal of seawater, rinsing of resin, and elution of resin into acid. For isotope samples these extraction techniques are performed manually, but the subsequent purification of Fe, Zn, and Cd by anion exchange chromatography is automated using the prepFAST. With these new methods, samples from the US GEOTRACES cruise GP16, in the eastern tropical South Pacific, are being analyzed. High concentrations of dissolved Fe are observed near the continental shelf and near submarine hydrothermal vents. Interestingly, isotope data show that dissolved Fe near the continental shelf generally has a δ56Fe close to 0 ‰. This δ56 Fe signature is suggestive of a non-reductive dissolution source for Fe, as Fe(II) released by reductive dissolution is typically closer to -2 ‰. Preliminary data show nutrient-type profiles for Zn and Cd, with Zn matching Si and Cd having a similar distribution to P. An increase in dissolved Zn near hydrothermal vents suggests a possible hydrothermal zinc source to the deep ocean. Continuing analysis of isotope data will reveal more about the source and biogeochemical cycling of these three chemically and biologically important trace metals throughout the eastern tropical Pacific Ocean.

Effects of bottom water dissolved oxygen variability on copper and lead fractionation in the sediments across the oxygen minimum zone, western continental margin of India.

PubMed

Chakraborty, Parthasarathi; Chakraborty, Sucharita; Jayachandran, Saranya; Madan, Ritu; Sarkar, Arindam; Linsy, P; Nath, B Nagender

2016-10-01

This study describes the effect of varying bottom-water oxygen concentration on geochemical fractionation (operational speciation) of Cu and Pb in the underneath sediments across the oxygen minimum zone (Arabian Sea) in the west coast of India. Both, Cu and Pb were redistributed among the different binding phases of the sediments with changing dissolved oxygen level (from oxic to hypoxic and close to suboxic) in the bottom water. The average lability of Cu-sediment complexes gradually decreased (i.e., stability increased) with the decreasing dissolved oxygen concentrations of the bottom water. Decreasing bottom-water oxygen concentration increased Cu association with sedimentary organic matter. However, Pb association with Fe/Mn-oxyhydroxide phases in the sediments gradually decreased with the decreasing dissolved oxygen concentration of the overlying bottom water (due to dissolution of Fe/Mn oxyhydroxide phase). The lability of Pb-sediment complexes increased with the decreasing bottom-water oxygen concentration. This study suggests that bottom-water oxygen concentration is one of the key factors governing stability and lability of Cu and Pb complexes in the underneath sediment. Sedimentary organic matter and Fe/Mn oxyhydroxide binding phases were the major hosting phases for Cu and Pb respectively in the study area. Increasing lability of Pb-complexes in bottom sediments may lead to positive benthic fluxes of Pb at low oxygen environment. Copyright © 2016 Elsevier B.V. All rights reserved.

The effect of iron content and dissolved O2 on dissolution rates of clinopyroxene at pH 5.8 and 25°C: Preliminary results

USGS Publications Warehouse

Hoch, A.R.; Reddy, M.M.; Drever, J.I.

1996-01-01

Dissolution experiments using augite (Mg0.87Ca0.85Fe0.19Na0.09Al0.03Si2O6) and diopside (Mg0.91Ca0.93Fe0.07Na0.03Al0.03Si2O6) were conducted in flow-through reactors (5-ml/h flow rate). A pH of 5.8 was maintained by bubbling pure CO2 through a solution of 0.01 M KHCO3 at 25°C. Two experiments were run for each pyroxene type. In one experiment dissolved O2 concentration in reactors was 0.6 (±0.1) ppm and in the second dissolved O2 was 1.5 (±0.1) ppm. After 60 days, augite dissolution rates (based on Si release) were approximately three times greater in the 1.5 ppm. dissolved O2 experiments than in the sealed experiments. In contrast, diopside dissolution rates were independent of dissolved O2 concentrations. Preliminary results from the augite experiments suggest that dissolution rate is directly related to oxidation of iron. This effect was not observed in experiments performed on iron-poor diopside. Additionally, dissolution rates of diopside were much slower than those of augite, again suggesting a relationship between Fe content, Fe oxidation and dissolution rates.

Dissolved metals and associated constituents in abandoned coal-mine discharges, Pennsylvania, USA. Part 2: Geochemical controls on constituent concentrations

USGS Publications Warehouse

Cravotta, C.A.

2008-01-01

Water-quality data for discharges from 140 abandoned mines in the Anthracite and Bituminous Coalfields of Pennsylvania reveal complex relations among the pH and dissolved solute concentrations that can be explained with geochemical equilibrium models. Observed values of pH ranged from 2.7 to 7.3 in the coal-mine discharges (CMD). Generally, flow rates were smaller and solute concentrations were greater for low-pH CMD samples; pH typically increased with flow rate. Although the frequency distribution of pH was similar for the anthracite and bituminous discharges, the bituminous discharges had smaller median flow rates; greater concentrations of SO4, Fe, Al, As, Cd, Cu, Ni and Sr; comparable concentrations of Mn, Cd, Zn and Se; and smaller concentrations of Ba and Pb than anthracite discharges with the same pH values. The observed relations between the pH and constituent concentrations can be attributed to (1) dilution of acidic water by near-neutral or alkaline ground water; (2) solubility control of Al, Fe, Mn, Ba and Sr by hydroxide, sulfate, and/or carbonate minerals; and (3) aqueous SO4-complexation and surface-complexation (adsorption) reactions. The formation of AlSO4+ and AlHSO42 + complexes adds to the total dissolved Al concentration at equilibrium with Al(OH)3 and/or Al hydroxysulfate phases and can account for 10-20 times greater concentrations of dissolved Al in SO4-laden bituminous discharges compared to anthracite discharges at pH of 5. Sulfate complexation can also account for 10-30 times greater concentrations of dissolved FeIII concentrations at equilibrium with Fe(OH)3 and/or schwertmannite (Fe8O8(OH)4.5(SO4)1.75) at pH of 3-5. In contrast, lower Ba concentrations in bituminous discharges indicate that elevated SO4 concentrations in these CMD sources could limit Ba concentrations by the precipitation of barite (BaSO4). Coprecipitation of Sr with barite could limit concentrations of this element. However, concentrations of dissolved Pb, Cu, Cd, Zn, and most other trace cations in CMD samples were orders of magnitude less than equilibrium with sulfate, carbonate, and/or hydroxide minerals. Surface complexation (adsorption) by hydrous ferric oxides (HFO) could account for the decreased concentrations of these divalent cations with increased pH. In contrast, increased concentrations of As and, to a lesser extent, Se with increased pH could result from the adsorption of these oxyanions by HFO at low pH and desorption at near-neutral pH. Hence, the solute concentrations in CMD and the purity of associated "ochres" formed in CMD settings are expected to vary with pH and aqueous SO4 concentration, with potential for elevated SO4, As and Se in ochres formed at low pH and elevated Cu, Cd, Pb and Zn in ochres formed at near-neutral pH. Elevated SO4 content of ochres could enhance the adsorption of cations at low pH, but decrease the adsorption of anions such as As. Such information on environmental processes that control element concentrations in aqueous samples and associated precipitates could be useful in the design of systems to reduce dissolved contaminant concentrations and/or to recover potentially valuable constituents in mine effluents.

Influence of humic acid imposed changes of ferrihydrite aggregation on microbial Fe(III) reduction

NASA Astrophysics Data System (ADS)

Amstaetter, Katja; Borch, Thomas; Kappler, Andreas

2012-05-01

Microbial reduction of Fe(III) minerals at neutral pH is faced by the problem of electron transfer from the cells to the solid-phase electron acceptor and is thought to require either direct cell-mineral contact, the presence of Fe(III)-chelators or the presence of electron shuttles, e.g. dissolved or solid-phase humic substances (HS). In this study we investigated to which extent the ratio of Pahokee Peat Humic Acids (HA) to ferrihydrite in the presence and absence of phosphate influences rates of Fe(III) reduction by Shewanella oneidensis MR-1 and the identity of the minerals formed. We found that phosphate generally decreased reduction rates by sorption to the ferrihydrite and surface site blocking. In the presence of low ferrihydrite concentrations (5 mM), the addition of HA helped to overcome this inhibiting effect by functioning as electron shuttle between cells and the ferrihydrite. In contrast, at high ferrihydrite concentrations (30 mM), the addition of HA did not lead to an increase but rather to a decrease in reduction rates. Confocal laser scanning microscopy images and ferrihydrite sedimentation behaviour suggest that the extent of ferrihydrite surface coating by HA influences the aggregation of the ferrihydrite particles and thereby their accessibility for Fe(III)-reducing bacteria. We further conclude that in presence of dissolved HA, iron reduction is stimulated through electron shuttling while in the presence of only sorbed HA, no stimulation by electron shuttling takes place. In presence of phosphate the stimulation effect did not occur until a minimum concentration of 10 mg/l of dissolved HA was reached followed by increasing Fe(III) reduction rates up to dissolved HA concentrations of approximately 240 mg/l above which the electron shuttling effect ceased. Not only Fe(III) reduction rates but also the mineral products changed in the presence of HA. Sequential extraction, XRD and 57Fe-Mössbauer spectroscopy showed that crystallinity and grain size of the magnetite produced by Fe(III) reduction in the presence of HA is lower than the magnetite produced in the absence of HA. In summary, this study shows that both the concentration of HA and Fe(III) minerals strongly influence microbial Fe(III) reduction rates and the mineralogy of the reduction products. Thus, deviations in iron (hydr)oxide reactivity with changes in aggregation state, such as HA induced ferrihydrite aggregation, need to be considered within natural environments.

Revisiting Mn and Fe removal in humic rich estuaries

NASA Astrophysics Data System (ADS)

Oldham, Véronique E.; Miller, Megan T.; Jensen, Laramie T.; Luther, George W.

2017-07-01

Metal removal by estuarine mixing has been studied for several decades, but few studies emphasize dissolved metal speciation and organic ligand complexation. Findings from the last decade indicate that metal-humic complexation can be significant for dissolved metals including Cu(II), Al(III) and Fe(III), but little consideration is given to the precipitation of these complexes with humic material at pH < 2. Given that total soluble metal analysis involves an acidification step for sample preservation, we show that Mn and other metal concentrations may have been underestimated in estuaries, especially when humic substance concentrations are high. A competitive ligand assay of selected samples from our study site, a coastal waterway bordered by wetlands (Broadkill River, DE), showed that Mn(III)-humic complexation is significant, and that some Mn(III)-L complexes precipitate during acidification. In the oxygenated surface waters of the Broadkill River, total dissolved Mn (dMnT) was up to 100% complexed to ambient ligands as Mn(III)-L, and we present evidence for humic-type Mn(III)-L complexes. The Mn(III) complexes were kinetically stabilized against Fe(II) reduction, even when [Fe(II)] was 17 times higher than [dMnT]. Unlike typical oceanic surface waters, [Fe(II)] > [Fe(III)-L] in surface waters, which may be attributed to high rates of photoreduction of Fe(III)-L complexes. Total [Mn(III)-L] ranged from 0.22 to 8.4 μM, in excess of solid MnOx (below 0.28 μM in all samples). Filtration of samples through 0.02 μm filters indicated that all Mn(III)-L complexes pass through the filters and were not colloidal species in contrast to dissolved Fe. Incubation experiments indicated that the reductive dissolution of solid MnOx by ambient ligands may be responsible for Mn(III) formation in this system. Unlike previous studies of estuarine mixing, which demonstrated metal removal during mixing, we show significant export of dMn and dissolved Fe (dFe) in the summer and fall of 2015. Thus, we propose that estuarine removal should be considered seasonal for dMn and dFe, with export in the summer and fall and removal during the winter.

Reactive-transport modeling of iron diagenesis and associated organic carbon remineralization in a Florida (USA) subterranean estuary

USGS Publications Warehouse

Roy, Moutusi; Martin, Jonathan B.; Smith, Christopher G.; Cable, Jaye E.

2011-01-01

Iron oxides are important terminal electron acceptors for organic carbon (OC) remineralization in subterranean estuaries, particularly where oxygen and nitrate concentrations are low. In Indian River Lagoon, Florida, USA, terrestrial Fe-oxides dissolve at the seaward edge of the seepage face and flow upward into overlying marine sediments where they precipitate as Fe-sulfides. The dissolved Fe concentrations vary by over three orders of magnitude, but Fe-oxide dissolution rates are similar across the 25-m wide seepage face, averaging around 0.21 mg/cm2/yr. The constant dissolution rate, but differing concentrations, indicate Fe dissolution is controlled by a combination of increasing lability of dissolved organic carbon (DOC) and slower porewater flow velocities with distance offshore. In contrast, the average rate constants of Fe-sulfide precipitation decrease from 21.9 × 10-8 s-1 to 0.64 × 10-8 s-1 from the shoreline to the seaward edge of the seepage face as more oxygenated surface water circulates through the sediment. The amount of OC remineralized by Fe-oxides varies little across the seepage face, averaging 5.34 × 10-2 mg/cm2/yr. These rates suggest about 3.4 kg of marine DOC was remineralized in a 1-m wide, shore-perpendicular strip of the seepage face as the terrestrial sediments were transgressed over the past 280 years. During this time, about 10 times more marine solid organic carbon (SOC) accumulated in marine sediments than were removed from the underlying terrestrial sediments. Indian River Lagoon thus appears to be a net sink for marine OC.

The role of alluvial aquifer sediments in attenuating a dissolved arsenic plume

USGS Publications Warehouse

Ziegler, Brady A.; Schreiber, Madeline E.; Cozzarelli, Isabelle M.

2017-01-01

In a crude-oil-contaminated sandy aquifer at the Bemidji site in northern Minnesota, biodegradation of petroleum hydrocarbons has resulted in release of naturally occurring As to groundwater under Fe-reducing conditions. This study used chemical extractions of aquifer sediments collected in 1993 and 2011–2014 to evaluate the relationship between Fe and As in different redox zones (oxic, methanogenic, Fe-reducing, anoxic-suboxic transition) of the contaminated aquifer over a twenty-year period. Results show that 1) the aquifer has the capacity to naturally attenuate the plume of dissolved As, primarily through sorption; 2) Fe and As are linearly correlated in sediment across all redox zones, and a regression analysis between Fe and As reasonably predicted As concentrations in sediment from 1993 using only Fe concentrations; 3) an As-rich “iron curtain,” associated with the anoxic-suboxic transition zone, migrated 30 m downgradient between 1993 and 2013 as a result of the hydrocarbon plume evolution; and 4) silt lenses in the aquifer preferentially sequester dissolved As, though As is remobilized into groundwater from sediment after reducing conditions are established. Using results of this study coupled with historical data, we develop a conceptual model which summarizes the natural attenuation of As and Fe over time and space that can be applied to other sites that experience As mobilization due to an influx of bioavailable organic matter.

The role of alluvial aquifer sediments in attenuating a dissolved arsenic plume.

PubMed

Ziegler, Brady A; Schreiber, Madeline E; Cozzarelli, Isabelle M

2017-09-01

In a crude-oil-contaminated sandy aquifer at the Bemidji site in northern Minnesota, biodegradation of petroleum hydrocarbons has resulted in release of naturally occurring As to groundwater under Fe-reducing conditions. This study used chemical extractions of aquifer sediments collected in 1993 and 2011-2014 to evaluate the relationship between Fe and As in different redox zones (oxic, methanogenic, Fe-reducing, anoxic-suboxic transition) of the contaminated aquifer over a twenty-year period. Results show that 1) the aquifer has the capacity to naturally attenuate the plume of dissolved As, primarily through sorption; 2) Fe and As are linearly correlated in sediment across all redox zones, and a regression analysis between Fe and As reasonably predicted As concentrations in sediment from 1993 using only Fe concentrations; 3) an As-rich "iron curtain," associated with the anoxic-suboxic transition zone, migrated 30m downgradient between 1993 and 2013 as a result of the hydrocarbon plume evolution; and 4) silt lenses in the aquifer preferentially sequester dissolved As, though As is remobilized into groundwater from sediment after reducing conditions are established. Using results of this study coupled with historical data, we develop a conceptual model which summarizes the natural attenuation of As and Fe over time and space that can be applied to other sites that experience As mobilization due to an influx of bioavailable organic matter. Copyright © 2017 Elsevier B.V. All rights reserved.

Net alkalinity and net acidity 2: Practical considerations

USGS Publications Warehouse

Kirby, C.S.; Cravotta, C.A.

2005-01-01

The pH, alkalinity, and acidity of mine drainage and associated waters can be misinterpreted because of the chemical instability of samples and possible misunderstandings of standard analytical method results. Synthetic and field samples of mine drainage having various initial pH values and concentrations of dissolved metals and alkalinity were titrated by several methods, and the results were compared to alkalinity and acidity calculated based on dissolved solutes. The pH, alkalinity, and acidity were compared between fresh, unoxidized and aged, oxidized samples. Data for Pennsylvania coal mine drainage indicates that the pH of fresh samples was predominantly acidic (pH 2.5-4) or near neutral (pH 6-7); ??? 25% of the samples had pH values between 5 and 6. Following oxidation, no samples had pH values between 5 and 6. The Standard Method Alkalinity titration is constrained to yield values >0. Most calculated and measured alkalinities for samples with positive alkalinities were in close agreement. However, for low-pH samples, the calculated alkalinity can be negative due to negative contributions by dissolved metals that may oxidize and hydrolyze. The Standard Method hot peroxide treatment titration for acidity determination (Hot Acidity) accurately indicates the potential for pH to decrease to acidic values after complete degassing of CO2 and oxidation of Fe and Mn, and it indicates either the excess alkalinity or that required for neutralization of the sample. The Hot Acidity directly measures net acidity (= -net alkalinity). Samples that had near-neutral pH after oxidation had negative Hot Acidity; samples that had pH < 6.3 after oxidation had positive Hot Acidity. Samples with similar pH values before oxidation had dissimilar Hot Acidities due to variations in their alkalinities and dissolved Fe, Mn, and Al concentrations. Hot Acidity was approximately equal to net acidity calculated based on initial pH and dissolved concentrations of Fe, Mn, and Al minus the initial alkalinity. Acidity calculated from the pH and dissolved metals concentrations, assuming equivalents of 2 per mole of Fe and Mn and 3 per mole of Al, was equivalent to that calculated based on complete aqueous speciation of FeII/FeIII. Despite changes in the pH, alkalinity, and metals concentrations, the Hot Acidities were comparable for fresh and most aged samples. A meaningful "net" acidity can be determined from a measured Hot Acidity or by calculation from the pH, alkalinity, and dissolved metals concentrations. The use of net alkalinity = (Alkalinitymeasured - Hot Aciditymeasured) to design mine drainage treatment can lead to systems with insufficient Alkalinity to neutralize metal and H+ acidity and is not recommended. The use of net alkalinity = -Hot Acidity titration is recommended for the planning of mine drainage treatment. The use of net alkalinity = (Alkalinitymeasured - Aciditycalculated) is recommended with some cautions. ?? 2005 Elsevier Ltd. All rights reserved.

Iron Biogeochemistry in the High Latitude North Atlantic Ocean.

PubMed

Achterberg, Eric P; Steigenberger, Sebastian; Marsay, Chris M; LeMoigne, Frédéric A C; Painter, Stuart C; Baker, Alex R; Connelly, Douglas P; Moore, C Mark; Tagliabue, Alessandro; Tanhua, Toste

2018-01-19

Iron (Fe) is an essential micronutrient for marine microbial organisms, and low supply controls productivity in large parts of the world's ocean. The high latitude North Atlantic is seasonally Fe limited, but Fe distributions and source strengths are poorly constrained. Surface ocean dissolved Fe (DFe) concentrations were low in the study region (<0.1 nM) in summer 2010, with significant perturbations during spring 2010 in the Iceland Basin as a result of an eruption of the Eyjafjallajökull volcano (up to 2.5 nM DFe near Iceland) with biogeochemical consequences. Deep water concentrations in the vicinity of the Reykjanes Ridge system were influenced by pronounced sediment resuspension, with indications for additional inputs by hydrothermal vents, with subsequent lateral transport of Fe and manganese plumes of up to 250-300 km. Particulate Fe formed the dominant pool, as evidenced by 4-17 fold higher total dissolvable Fe compared with DFe concentrations, and a dynamic exchange between the fractions appeared to buffer deep water DFe. Here we show that Fe supply associated with deep winter mixing (up to 103 nmol m -2 d -1 ) was at least ca. 4-10 times higher than atmospheric deposition, diffusive fluxes at the base of the summer mixed layer, and horizontal surface ocean fluxes.

Distinguishing iron-reducing from sulfate-reducing conditions

USGS Publications Warehouse

Chapelle, F.H.; Bradley, P.M.; Thomas, M.A.; McMahon, P.B.

2009-01-01

Ground water systems dominated by iron- or sulfate-reducing conditions may be distinguished by observing concentrations of dissolved iron (Fe2+) and sulfide (sum of H2S, HS-, and S= species and denoted here as "H2S"). This approach is based on the observation that concentrations of Fe2+ and H2S in ground water systems tend to be inversely related according to a hyperbolic function. That is, when Fe2+ concentrations are high, H2S concentrations tend to be low and vice versa. This relation partly reflects the rapid reaction kinetics of Fe2+ with H2S to produce relatively insoluble ferrous sulfides (FeS). This relation also reflects competition for organic substrates between the iron- and the sulfate-reducing microorganisms that catalyze the production of Fe2+ and H 2S. These solubility and microbial constraints operate in tandem, resulting in the observed hyperbolic relation between Fe2+ and H 2S concentrations. Concentrations of redox indicators, including dissolved hydrogen (H2) measured in a shallow aquifer in Hanahan, South Carolina, suggest that if the Fe2+/H2S mass ratio (units of mg/L) exceeded 10, the screened interval being tapped was consistently iron reducing (H2 ???0.2 to 0.8 nM). Conversely, if the Fe 2+/H2S ratio was less than 0.30, consistent sulfate-reducing (H2 ???1 to 5 nM) conditions were observed over time. Concomitantly high Fe2+ and H2S concentrations were associated with H2 concentrations that varied between 0.2 and 5.0 nM over time, suggesting mixing of water from adjacent iron- and sulfate-reducing zones or concomitant iron and sulfate reduction under nonelectron donor-limited conditions. These observations suggest that Fe2+/H2S mass ratios may provide useful information concerning the occurrence and distribution of iron and sulfate reduction in ground water systems. ?? 2009 National Ground Water Association.

Phosphorus losses from agricultural land to natural waters are reduced by immobilization in iron-rich sediments of drainage ditches.

PubMed

Baken, Stijn; Verbeeck, Mieke; Verheyen, Dries; Diels, Jan; Smolders, Erik

2015-03-15

Redox reactions involving iron (Fe) strongly affect the mobility of phosphorus (P) and its migration from agricultural land to freshwater. We studied the transfer of P from groundwater to open drainage ditches in an area where, due to Fe(II) rich groundwater, the sediments of these ditches contain accumulated Fe oxyhydroxides. The average P concentrations in the groundwater feeding two out of three studied drainage ditches exceeded environmental limits for freshwaters by factors 11 and 16, but after passing through the Fe-rich sediments, the P concentrations in the ditch water were below these limits. In order to identify the processes which govern Fe and P mobility in these systems, we used diffusive equilibration in thin films (DET) to measure the vertical concentration profiles of P and Fe in the sediment pore water and in the ditchwater. The Fe concentrations in the sediment pore water ranged between 10 and 200 mg L(-1) and exceeded those in the inflowing groundwater by approximately one order of magnitude, due to reductive dissolution of Fe oxyhydroxides in the sediment. The dissolved P concentrations only marginally increased between groundwater and sediment pore water. In the poorly mixed ditchwater, the dissolved Fe concentrations decreased towards the water surface due to oxidative precipitation of fresh Fe oxyhydroxides, and the P concentrations decreased more sharply than those of Fe. These observations support the view that the dynamics of Fe and P are governed by reduction reactions in the sediment and by oxidation reactions in the ditchwater. In the sediment, reductive dissolution of P-containing Fe oxyhydroxides causes more efficient solubilization of Fe than of P, likely because P is buffered by adsorption on residual Fe oxyhydroxides. Conversely, in the ditchwater, oxidative precipitation causes more efficient immobilization of P than of Fe, due to ferric phosphate formation. The combination of these processes yields a natural and highly efficient sink for P. It is concluded that, in Fe-rich systems, the fate of P at the sediment-water interface is determined by reduction and oxidation of Fe. Copyright © 2015 Elsevier Ltd. All rights reserved.

Leachable particulate iron in the Columbia River, estuary, and near-field plume

NASA Astrophysics Data System (ADS)

Lippiatt, Sherry M.; Brown, Matthew T.; Lohan, Maeve C.; Berger, Carolyn J. M.; Bruland, Kenneth W.

2010-03-01

This study examines the distribution of leachable particulate iron (Fe) in the Columbia River, estuary, and near-field plume. Surface samples were collected during late spring and summer of 2004-2006 as part of four River Influence on Shelf Ecosystems (RISE) cruises. Tidal amplitude and river flow are the primary factors influencing the estuary leachable particulate Fe concentrations, with greater values during high flow and/or spring tides. Near the mouth of the estuary, leachable particulate Fe [defined as the particulate Fe solubilized with a 25% acetic acid (pH 2) leach containing a weak reducing agent to reduce Fe oxyhydroxides and a short heating step to access intracellular Fe] averaged 770 nM during either spring tide or high flow, compared to 320 nM during neap tide, low flow conditions. In the near-field Columbia River plume, elevated leachable particulate Fe concentrations occur during spring tides and/or higher river flow, with resuspended shelf sediment as an additional source to the plume during periods of coastal upwelling and spring tides. Near-field plume concentrations of leachable particulate Fe (at a salinity of 20) averaged 660 nM during either spring tide or high flow, compared to 300 nM during neap tide, low flow conditions. Regardless of tidal amplitude and river flow, leachable particulate Fe concentrations in both the river/estuary and near-field plume are consistently one to two orders of magnitude greater than dissolved Fe concentrations. The Columbia River is an important source of reactive Fe to the productive coastal waters off Oregon and Washington, and leachable particulate Fe is available for solubilization following biological drawdown of the dissolved phase. Elevated leachable Fe concentrations allow coastal waters influenced by the Columbia River plume to remain Fe-replete and support phytoplankton production during the spring and summer seasons.

Surface chemistry of bulk nanocrystalline pure iron and electrochemistry study in gas-flow physiological saline.

PubMed

Nie, F L; Zheng, Y F

2012-07-01

Conventional microcrystalline pure iron (MC-Fe) becomes a new candidate as biodegradable metals, which has the insufficient physical feature and inferior biodegradation behavior. Novel bulk nanocrystalline pure iron (NC-Fe) was fabricated via equal channel angular pressing technique in the present work to overcome these problems. The contact angle test with water and glycerol droplets shows a smaller angle (though >90°) of NC-Fe than that of MC-Fe, which implies a lower surface energy of NC-Fe. The surface roughness of NC-Fe increased greatly than that of MC-Fe. A further comparative study of corrosion and electrochemistry performance between NC-Fe and its original MC-Fe was investigated in physiological saline with different dissolved oxygen concentration, aiming to in vitro simulate the corrosion process of coronary stent occurred in physiological environment. The electrochemical impedance spectra analysis and anodic polarization measurements indicated that the NC-Fe exhibited higher corrosion resistance than that of the MC-Fe; meanwhile obvious enhanced corrosion resistance with the decrement of dissolved oxygen concentration was observed. Related equivalent circuit model and surface reconstruction process were further discussed, and the degradation mechanism of the MC-Fe and NC-Fe were finally established. Copyright © 2012 Wiley Periodicals, Inc.

Geochemical modeling of iron, sulfur, oxygen and carbon in a coastal plain aquifer

NASA Astrophysics Data System (ADS)

Brown, C. J.; Schoonen, M. A. A.; Candela, J. L.

2000-11-01

Fe(III) reduction in the Magothy aquifer of Long Island, NY, results in high dissolved-iron concentrations that degrade water quality. Geochemical modeling was used to constrain iron-related geochemical processes and redox zonation along a flow path. The observed increase in dissolved inorganic carbon is consistent with the oxidation of sedimentary organic matter coupled to the reduction of O 2 and SO 42- in the aerobic zone, and to the reduction of SO 42- in the anaerobic zone; estimated rates of CO 2 production through reduction of Fe(III) were relatively minor by comparison. The rates of CO 2 production calculated from dissolved inorganic carbon mass transfer (2.55×10 -4 to 48.6×10 -4 mmol l -1 yr-1) generally were comparable to the calculated rates of CO 2 production by the combined reduction of O 2, Fe(III) and SO 42- (1.31×10 -4 to 15×10 -4 mmol l -1 yr-1). The overall increase in SO 42- concentrations along the flow path, together with the results of mass-balance calculations, and variations in δ34S values along the flow path indicate that SO 42- loss through microbial reduction is exceeded by SO 42- gain through diffusion from sediments and through the oxidation of FeS 2. Geochemical and microbial data on cores indicate that Fe(III) oxyhydroxide coatings on sediment grains in local, organic carbon- and SO 42--rich zones have been depleted by microbial reduction and resulted in localized SO 42--reducing zones in which the formation of iron disulfides decreases dissolved iron concentrations. These localized zones of SO 42- reduction, which are important for assessing zones of low dissolved iron for water-supply development, could be overlooked by aquifer studies that rely only on groundwater data from well-water samples for geochemical modeling.

Insights into iron sources and pathways in the Amazon River provided by isotopic and spectroscopic studies

NASA Astrophysics Data System (ADS)

Mulholland, Daniel Santos; Poitrasson, Franck; Boaventura, Geraldo Resende; Allard, Thierry; Vieira, Lucieth Cruz; Santos, Roberto Ventura; Mancini, Luiz; Seyler, Patrick

2015-02-01

The present study investigated the weathering and transport mechanisms of Fe in the Amazon River. A particular emphasis was placed on Fe partitioning, speciation, and isotopic fractionation in the contrasting waters of the Solimões and Negro rivers and their mixing zone at the beginning of the Amazon River. Samples collected in the end-member rivers and thirteen sites distributed throughout the mixing zone were processed through frontal vacuum filtration and tangential-flow ultrafiltration to separate the different suspended solid fractions, i.e., particulate (P > 0.45 μm and P > 0.22 μm), colloidal (0.22 μm > C > 5 kDa) and truly dissolved elements (TD < 5 kDa). The Fe isotopic composition and electron paramagnetic resonance (EPR) species were measured on these different pore-sized fractions. The acidic and organo-Fe-rich waters of the Negro River displayed dissolved and colloidal fractions enriched in heavy isotopes (∼1.2‰, in δ57Fe values relative to IRMM-14), while the particulate fractions yielded light isotopic compositions of -0.344‰ for P > 0.22 μm and -0.104‰ for P > 0.45 μm fractions). The mineral particulate-rich waters of the Solimões River had dissolved and colloidal fractions with light isotopic composition (-0.532‰ and -0.176‰, respectively), whereas the particulate fractions yielded δ57Fe values close to those of the continental crust (i.e., -0.029‰ for P > 0.22 μm and 0.028‰ for P > 0.45 μm). Ten kilometers downstream from the Negro and Solimões junction, the concentrations of colloidal and dissolved Fe species deviate markedly from conservative mixing. A maximum Fe loss of 43 μg/L (i.e., 50% of the dissolved and colloidal Fe) is observed 110 km downstream from the rivers junction. The contrasting Negro and Solimões Rivers isotopic compositions along the pore-sized water fractions is attributable to the biogeochemical processes involving different types of upland soils and parental materials. For instance, the isotopic composition of colloidal and dissolved Fe from the Negro River are consistent with Fe oxidation and complexation mechanisms at the interface between waterlogged podzols and river networks, as supported by strong organo-Fe complexes signals observed by EPR. Conversely, the particulate and colloidal fractions from the Solimões River have δ57Fe consistent with strong mechanical erosion in the Andean Cordillera and upland soils, as evidenced by high concentrations of Fe3+-oxides sensu lato measured by EPR. The massive dissolved and colloidal Fe removal is associated with the evolution of the physical and chemical composition of the waters (i.e., ionic strength) during mixing, which influences organo-Fe3+ and Fe3+-oxyhydroxides stability. Several models are discussed to explain Fe non-conservative behavior, including dissociation of organo-Fe complexes and the subsequent formation of solid Fe3+-oxyhydroxides and semiquinone free radicals, as evidenced by EPR spectra demonstrating that organo-Fe signals decrease as Fe3+-oxyhydroxides and free radicals signals increase. As in estuarine regions, the mechanisms involving Fe transfer and loss in the mixing zone has a negligible effect on the bulk water Fe isotopic composition. This result suggests that a tropical basin similar to the Amazon River Basin delivers to the ocean waters with an Fe isotopic composition similar to that of the Earth's continental crust.

Dissolved iron and iron(II) distributions beneath the pack ice in the East Antarctic (120°E) during the winter/spring transition

NASA Astrophysics Data System (ADS)

Schallenberg, Christina; van der Merwe, Pier; Chever, Fanny; Cullen, Jay T.; Lannuzel, Delphine; Bowie, Andrew R.

2016-09-01

Distributions of dissolved iron (dFe) and its reduced form, Fe(II), to a depth of 1000 m were investigated under the seasonal pack ice off East Antarctica during the Sea Ice Physics and Ecosystem experiment (SIPEX-2) sea-ice voyage in September-October 2012. Concentrations of dFe were elevated up to five-fold relative to Southern Ocean background concentrations and were spatially variable. The mean dFe concentration was 0.44±0.4 nM, with a range from 0.09 to 3.05 nM. Profiles of dFe were more variable within and among stations than were macronutrients, suggesting that coupling between these biologically-essential elements was weak at the time of the study. Brine rejection and drainage from sea ice are estimated to be the dominant contributors to elevated dFe concentrations in the mixed layer, but mass budget considerations indicate that estimated dFe fluxes from brine input alone are insufficient to account for all observed dFe. Melting icebergs and shelf sediments are suspected to provide the additional dFe. Fe(II) was mostly below the detection limit but elevated at depth near the continental shelf, implying that benthic processes are a source of reduced Fe in bottom waters. The data indicate that dFe builds up under the seasonal sea-ice cover during winter and that reduction of Fe may be hampered in early spring by several factors such as lack of electron donors, low biological productivity and inadequate light below the sea ice. The accumulated dFe pool in the mixed layer is expected to contribute to the formation of the spring bloom as the ice retreats.

Dissolved heavy metal concentrations of the Kralkızı, Dicle and Batman dam reservoirs in the Tigris River basin, Turkey.

PubMed

Varol, Memet

2013-10-01

Water samples were collected at monthly intervals during 1 year of monitoring from Kralkızı, Dicle and Batman dam reservoirs in the Tigris River basin to assess the concentrations of dissolved heavy metals and to determine their spatial and seasonal variations. The results indicated that dissolved heavy metal concentrations in the reservoirs were very low, reflecting the natural background levels. The lowest total metal concentrations in the three dam reservoirs were detected at sampling sites close to the dam wall. However, the highest total concentrations were observed at sites, which are located at the entrance of the streams to the reservoirs. Fe, Cr and Ni were the most abundant elements in the reservoirs, whereas Cd and As were the less abundant. The mean concentrations of dissolved metals in the dam reservoirs never exceeded the maximum permitted concentrations established by EC (European Community), WHO and USEPA drinking water quality guidelines. All heavy metals showed significant seasonal variations. As, Cd, Cr, Cu, Fe, Ni and Pb displayed higher values in the dry season, while higher values for Zn in the wet season. Cluster analysis grouped all ten sampling sites into three clusters. Clusters 1 and 2, and cluster 3 corresponded to relatively low polluted and moderate polluted regions, respectively. PCA/FA demonstrated the dissolved metals in the dam reservoirs controlled by natural sources. Copyright © 2013 Elsevier Ltd. All rights reserved.

Distal transport of dissolved hydrothermal iron in the deep South Pacific Ocean

PubMed Central

Fitzsimmons, Jessica N.; Boyle, Edward A.; Jenkins, William J.

2014-01-01

Until recently, hydrothermal vents were not considered to be an important source to the marine dissolved Fe (dFe) inventory because hydrothermal Fe was believed to precipitate quantitatively near the vent site. Based on recent abyssal dFe enrichments near hydrothermal vents, however, the leaky vent hypothesis [Toner BM, et al. (2012) Oceanography 25(1):209–212] argues that some hydrothermal Fe persists in the dissolved phase and contributes a significant flux of dFe to the global ocean. We show here the first, to our knowledge, dFe (<0.4 µm) measurements from the abyssal southeast and southwest Pacific Ocean, where dFe of 1.0–1.5 nmol/kg near 2,000 m depth (0.4–0.9 nmol/kg above typical deep-sea dFe concentrations) was determined to be hydrothermally derived based on its correlation with primordial 3He and dissolved Mn (dFe:3He of 0.9–2.7 × 106). Given the known sites of hydrothermal venting in these regions, this dFe must have been transported thousands of kilometers away from its vent site to reach our sampling stations. Additionally, changes in the size partitioning of the hydrothermal dFe between soluble (<0.02 µm) and colloidal (0.02–0.4 µm) phases with increasing distance from the vents indicate that dFe transformations continue to occur far from the vent source. This study confirms that although the southern East Pacific Rise only leaks 0.02–1% of total Fe vented into the abyssal Pacific, this dFe persists thousands of kilometers away from the vent source with sufficient magnitude that hydrothermal vents can have far-field effects on global dFe distributions and inventories (≥3% of global aerosol dFe input). PMID:25349389

Water quality impacts of hydraulic-fracturing chemicals observed in a permeable, quartz-sand aquifer

NASA Astrophysics Data System (ADS)

Kent, D. B.; LeBlanc, D. R.; Smith, R. L.

2012-12-01

A pilot scale experiment was conducted on western Cape Cod, Massachusetts to test the use of hydraulic fracturing (HF) for emplacing permeable reactive barriers (PRB) where the water table is too far below land surface to use standard excavation methods. Two PRB were emplaced 24 to 36 meters below land surface in a plume with low concentrations of perchloroethylene in oxic, mildly acidic groundwater with low concentrations of dissolved salts. The granular aquifer sediments consist of permeable sands and gravels. Quartz comprises greater than 90% by weight of the aquifer sediments but chemical reactivity of the sediments is controlled by micrometer-scale chlorite and illite and nanometer-scale aluminum-substituted goethite. HF fluids contained guar gum (gelling agent), cellulose enzyme and acetic acid (breakers), sodium borate (cross-linker), potassium (K) carbonate (pH adjustor), and sodium (Na) chloride (tracer). Water-quality impacts within about 20 meters of the PRB were monitored over a 1.7-year period following HF. Arrival of HF-chemicals was marked by an increase in boron (B) from ambient concentrations of 6 uM to >800 uM. B concentrations rose for approximately 50 days, much longer than the 22-day period over which HF was conducted. B concentrations subsequently decreased but remained 2-3 times above background concentrations for almost one year. Elevated Na and K concentrations in the HF fluids drove sorption (including ion exchange) reactions resulting in transient increases in naturally occurring major, minor, and trace cations up to 20 to 50 times background concentrations. Increases in dissolved organic carbon (DOC) and decreases in dissolved oxygen (DO) concentrations were observed as B concentrations increased. DOC concentration subsequently decreased but remained significantly above background. DO concentrations remained below detection. Dissolved iron (Fe) and manganese (Mn) concentrations increased as DO concentrations decreased below detection and remained elevated 1.7 years after HF. Reactions with Fe in the PRB may have contributed to the observed Fe concentrations but Mn was likely released from the aquifer sediments. Fe and Mn concentrations remained elevated throughout the sampling period. Dissolved arsenic concentrations increased after anaerobic conditions were established from below detection to 0.3-0.5 uM. HF fluids contained only a subset of the chemicals used in typical HF stimulations and aquifer sediments were likely less reactive than aquifer solids at other sites. Despite these differences, several findings have applicability to other sites. B is a potentially useful tracer of intrusion of HF fluids into aquifers, but elevated concentrations may be short-lived. Sorption reactions driven by differences in dissolved salt concentrations between HF fluids and ambient groundwater result in changes in cation concentrations, including barium and strontium. Organic compounds in HF fluids may drive aerobic aquifers anaerobic. Anaerobic conditions may lead to mobilization of naturally occurring contaminants like arsenic, whose reduced forms are more mobile than oxidized forms.

Geochemical controls of elevated arsenic concentrations in groundwater, Ester Dome, Fairbanks district, Alaska

USGS Publications Warehouse

Verplanck, P.L.; Mueller, S.H.; Goldfarb, R.J.; Nordstrom, D. Kirk; Youcha, E.K.

2008-01-01

Ester Dome, an upland area near Fairbanks, Alaska, was chosen for a detailed hydrogeochemical study because of the previously reported elevated arsenic in groundwater, and the presence of a large set of wells amenable to detailed sampling. Ester Dome lies within the Fairbanks mining district, where gold-bearing quartz veins, typically containing 2-3??vol.% sulfide minerals (arsenopyrite, stibnite, and pyrite), have been mined both underground and in open cuts. Gold-bearing veins on Ester Dome occur in shear zones and the sulfide minerals in these veins have been crushed to fine-grained material by syn- or post-mineralization movement. Groundwater at Ester Dome is circumneutral, Ca-HCO3 to Ca-SO4 type, and ranges from dilute (specific conductance of 48????S/cm) to more concentrated (specific conductance as high as 2070????S/cm). In general, solute concentrations increase down hydrologic gradient. Redox species indicate that the groundwaters range from oxic to sub-oxic (low dissolved oxygen, Fe(III) reduction, no SO4 reduction). Waters with the highest Fe concentrations, as high as 10.7??mg/L, are the most anoxic. Dissolved As concentrations range from < 1 to 1160????g/L, with a median value of 146????g/L. Arsenic concentrations are not correlated with specific conductance or Fe concentrations, suggesting that neither groundwater residence time, nor reductive dissolution of iron oxyhydroxides, control the arsenic chemistry. Furthermore, As concentrations do not covary with other constituents that form anions and oxyanions in solution (e.g., HCO3, Mo, F, or U) such that desorption of arsenic from clays or oxides also does not control arsenic mobility. Oxidation of arsenopyrite and dissolution of scorodite, in the near-surface environment appears to be the primary control of dissolved As in this upland area. More specifically, the elevated As concentrations are spatially associated with sulfidized shear zones and localities of gold-bearing quartz veins. Consistent with this interpretation, elevated dissolved Sb concentrations (as high as 59????g/L), also correlated with occurrences of hypogene sulfide minerals, were measured in samples with high dissolved As concentrations.

Iron dynamics: Transformation of Fe(II)/Fe(III) during injection of natural organic matter in a sandy aquifer

NASA Astrophysics Data System (ADS)

Liang, Liyuan; McCarthy, John F.; Jolley, Louwanda W.; McNabb, J. Andrew; Mehlhorn, Tonia L.

1993-05-01

The dynamics of dissolved, colloidal, and deposited iron phases were examined during a forced-gradient field experiment. The experiment involved the injection of oxygenated water containing high levels of natural organic matter (NOM) into a sandy aquifer. The initial redox potential of the aquifer favored Fe(II) in the groundwater. The changes in the concentrations of Fe(II) and Fe(III) were observed in sampling wells. Under the increased dissolved oxygen (DO) conditions, Fe(II) oxygenation was rapid, resulting in the formation of Fe(III) (hydr) oxide colloids. The oxidation follows the rate law as given in STUMM and MORGAN (1981): d[ Fe(II)] /dt = - k obs[ O2( aq)] /[ H+] 2[ Fe(II)] , with a rate constant, kobs to be 1.9 × 10 -12 M min -1. For an averaged pH and DO of the groundwater, the half time of Fe(II) oxidation is 49 h. The NOM was postulated to stabilize the newly formed colloids, thereby increasing the turbidity in the groundwater. The additional increase in the colloidal fraction of Fe(III) oxide suggested that transport of the colloidal particles was occurring. At those locations where DO remained constantly low, the turbidity increase was moderate, and up to 80% of Fe(III) was in the dissolved phase (< 3000 mol. wt). The latter observation was attributed to the presence of NOM, forming Fe(III)-organic complexes. In addition, NOM may play a role in the oxygen consumption through a Fe(II)/Fe(III) catalyzed oxidation of organic matter as outlined by STUMM and MORGAN (1981, p. 469). In this mechanism, Fe(II) oxidation is slow, maintaining a near constant Fe(II) concentration, in agreement with field data. The overall increase in Fe(III) under low DO conditions was postulated to be a combination of (1) slow oxidation, (2) ligand-promoted and catalytic dissolution of deposited iron phases, and (3) the transport of newly formed iron oxide colloids along flow paths.

Dissolved trace and minor elements in cryoconite holes and supraglacial streams, Canada Glacier, Antarctica

NASA Astrophysics Data System (ADS)

Fortner, Sarah K.; Lyons, W. Berry

2018-04-01

Here we present a synthesis of the trace element chemistry in melt on the surface Canada Glacier, Taylor Valley, McMurdo Dry Valleys (MDV), Antarctica ( 78°S). The MDV is largely ice-free. Low accumulation rates, strong winds, and proximity to the valley floor make these glaciers dusty in comparison to their inland counterparts. This study examines both supraglacial melt streams and cryoconite holes. Supraglacial streams on the lower Canada Glacier have median dissolved (<0.4 µm) concentrations of Fe, Mn, As, Cu, and V of 71.5, 75.5, 3.7, 4.6, and 4.3 nM. All dissolved Cd concentrations and the vast majority of Pb values are below our analytical detection (i.e. 0.4 and 0.06 nM). Chemical behavior did not follow similar trends for eastern and western draining waters. Heterogeneity likely reflects distinctions eolian deposition, rock:water ratios, and hydrologic connectivity. Future increases in wind-delivered sediment will likely drive dynamic responses in melt chemistry. For elements above detection limits, dissolved concentrations in glacier surface melt are within an order of magnitude of concentrations observed in proglacial streams (i.e. flowing on the valley floor). This suggests that glacier surfaces are an important source of downstream chemistry. The Fe enrichment of cryoconite water relative to N, P, or Si exceeds enrichment observed in marine phytoplankton. This suggests that the glacier surface is an important source of Fe to downstream ecosystems.

Role of Siderophores in Dissimilatory Iron Reduction in Arctic Soils : Effect of Direct Amendment of Siderophores to Arctic Soil

NASA Astrophysics Data System (ADS)

Srinivas, A. J.; Dinsdale, E. A.; Lipson, D.

2014-12-01

Dissimilatory iron reduction (DIR), where ferric iron (Fe3+) is reduced to ferrous iron (Fe2+) anaerobically, is an important respiratory pathway used by soil bacteria. DIR contributes to carbon dioxide (CO2) efflux from the wet sedge tundra biome in the Arctic Coastal Plain (ACP) in Alaska, and could competitively inhibit the production of methane, a stronger greenhouse gas than CO2, from arctic soils. The occurrence of DIR as a dominant anaerobic process depends on the availability of substantial levels of Fe3+ in soils. Siderophores are metabolites made by microbes to dissolve Fe3+ from soil minerals in iron deficient systems, making Fe3+ soluble for micronutrient uptake. However, as the ACP is not iron deficient, siderophores in arctic soils may play a vital role in anaerobic respiration by dissolving Fe3+ for DIR. We studied the effects of direct siderophore addition to arctic soils through a field study conducted in Barrow, Alaska, and a laboratory incubation study conducted at San Diego State University. In the field experiment, 50μM deferroxamine mesylate (a siderophore), 50μM trisodium nitrilotriacetate (an organic chelator) or an equal volume of water was added to isolated experimental plots, replicated in clusters across the landscape. Fe2+ concentrations were measured in soil pore water samples collected periodically to measure DIR over time in each. In the laboratory experiment, frozen soil samples obtained from drained thaw lake basins in the ACP, were cut into cores and treated with the above-mentioned compounds to the same final concentrations. Along with measuring Fe2+ concentrations, CO2 output was also measured to monitor DIR over time in each core. Experimental addition of siderophores to soils in both the field and laboratory resulted in increased concentrations of soluble Fe3+ and a sustained increase in Fe2+concentrations over time, along with increased respiration rates in siderophore-amended cores. These results show increased DIR in siderophore treated cores compared to the other treatments. From the results of these experiments, we conclude that arctic soil microbes can use siderophores to maintain a pool of dissolved Fe3+ for DIR. This study provides insight into the mechanisms of DIR in this ecosystem, and has relevance for understanding anaerobic soil respiration in the Arctic.

Redox speciation of dissolved iron in the northeastern atlantic ocean.

NASA Astrophysics Data System (ADS)

Ussher, S. J.; Achterberg, E. P.; Worsfold, P. J.

2003-04-01

Dissolved iron (<0.2 micron) and iron(II) (<0.2 micron) distributions were determined during the Iron from Below and Iron from Above research cruises in the North Eastern Atlantic Ocean. The cruises were part of the EU Ironages project. Iron(II) was measured on-board ship using an iron(II) specific, automated flow injection analyser with luminol chemiluminescence detection [1]. Total dissolved iron (DFe) was determined in a land-based laboratory, using the same FI technique but with prior reduction of iron(III) to iron(II) [2]. The limits of detection for the methods were 5 -15 pM and 35 pM respectively, the analysis time was 8 - 10 minutes per sample (minimum of 3 replicates). The Iron from Below expedition took place over the European Continental Shelf, 200 km South West of Brittany (France) in March 2002. A transect between 47.61°N, 4.24°W and 46.00°N, 8.01°W was completed. Over the transect, the depth increased from 100 m to 5000 m. Iron(II) concentrations ranged between 10 and 100 pM and DFe between 0.2 and 1 nM, with the higher concentrations (Fe(II) ca. > 50 pM and DFe ca. > 0.8 nM) generally found in the shallow shelf waters. These observations imply that benthic inputs and sediment resuspension may form important inputs of dissolved iron and iron(II) in the shelf waters. Iron speciation measurements were also made for underway surface and shallow cast samples during the Iron from Above cruise October 2002. Fe(II) and DFe concentrations were typically 5 to 50 pM and 0.2 to 0.6 nM, respectively. Sampling was carried out within a grid in the Canary Basin around 5 degrees W of the Canary Islands, an area assumed to be strongly influenced by the Saharan dust plume. Observed Fe(II) concentrations are compared and ratioed to the DFe concentrations, and indicate that iron(II) forms an important fraction (between 5 and 15%) of the total dissolved iron concentration in the study areas. Data plots for surface samples are presented with the corresponding physical oceanographic and solar irradiance data. The concentrations of Fe(II) observed during our studies exceed the values predicted from thermodynamic equilibrium modelling. This indicates that there is a steady supply of Fe(II) (possibly from photoreduction and/or biological origins) and/or Fe(II) is prevented from oxidation through stabilisation mechanisms (possibly by organic ligands). [1] A. R. Bowie, E. P. Achterberg, P. N. Sedwick, S. Ussher, P. J. Worsfold, Environ. Sci. Technol., 36, (2002) 4600. [2] A. R. Bowie, E. P. Achterberg, R. F. C. Mantoura, P. J. Worsfold, Anal. Chim. Acta, 377, (1998) 113.

Phase transition of Fe oxides under reducing condition and its relation with the As behavior

NASA Astrophysics Data System (ADS)

Choi, S. H.; Kim, S. H.; Jeong, G. Y.; Kim, K.

2014-12-01

Fe oxides are very common in the earth's crust and easily transform into other minerals such as magnetite and siderite under reducing conditions by microbial reactions. It is well known that As concentrations in groundwater is strongly regulated by adsorption onto Fe oxides. Even though some studies have suggested that the formation of siderite can also control the As concentration, direct evidences are not sufficient. In this study, we performed microbial incubation experiments to see the phase transition of As-rich Fe oxides under anoxic condition and to see how the water As concentrations are controlled accordingly. Three experiments were performed by changing organic carbon concentrations. Natural groundwaters and yeast extracts were used for the sources of microorganisms and organic carbon. Seven reactors were prepared for each experiment and opened one by one to observe the changes of the water chemistry and solid phases for 60 days. The formation of magnetite was observed at the early stage of each experiment. Siderite was formed at the later stage only when the dissolved organic carbon concentrations were high (donor/accepter molar ratio = 1.5). Goethite and hematite, instead of siderite, were formed from the experiment using low organic carbon concentration (donor/accepter molar ratio = 0.75). It is likely that dissolved ferrous ion adsorbs onto the Fe oxides and recrystallizes into hematite and goethite when the DOC concentration was low. As concentrations were generally very low in the water (normally 10 ug/L) and we could not find any relations with the Fe minerals formed by anoxic microbial reactions, maybe due to high Fe oxide/water ratio of our experiments. The sequential extraction analysis indicated that most of the As in solids are mostly associated with Fe-oxides and organic matters. The As bound to carbonates were very low even in the precipitates containing siderite due to low As concentrations in the water where the siderite formed. Further experiments precipitating siderite in the water with high As concentrations are required.

Estimating production and consumption of solid reactive Fe phases in marine sediments from concentration profiles

EPA Science Inventory

1D diffusion models may be used to estimate rates of production and consumption of dissolved metabolites in marine sediments, but are applied less often to the solid phase. Here we used a numerical inverse method to estimate solid phase Fe(III) and Fe(II) consumption and product...

Response of Phytoplankton Iron Contents to Gradients in Iron Availability in the California Current System

NASA Astrophysics Data System (ADS)

Twining, B. S.; Jacquot, J. E.; Rauschenberg, S.; Enright, J.; Marchetti, A.; Cohen, N.; Brown, M.; Parker, C.; Bruland, K. W.

2016-02-01

Iron is a critical micronutrient that controls primary production in large swaths of the global ocean. Experiments with laboratory cultures indicate that phytoplankton differ in their ability to compete for and store Fe in response to varying ambient Fe concentrations. However there are very few measurements of the physiological responses of natural phytoplankton populations to gradients in Fe availability. Incubation experiments were conducted off the coast of California and Oregon at two sites characterized by a 10-fold difference in dissolved Fe (0.3 and 3 nM). In each experiment, incubation water was amended with either dissolved Fe (5-10 nM), the model siderophore desferrioxamine B (DFB; 200 nM), or left unamended. Iron contents of three abundant diatom groups (Chaetoceros sp. and large and small pennate diatoms) were monitored by synchrotron X-ray fluorescence, along with dissolved and bulk particulate trace metals and macronutrients over the course of 3 days. Transcriptomic samples were also collected at daily timepoints to assess molecular responses. Added dissolved Fe was drawn down in both experiments, while DFB appeared to solubilize a fraction of ambient particulate Fe in the high-Fe experiment. Iron quotas of unamended diatoms were nearly 10-fold higher under high-Fe conditions. Quotas increased in response to added Fe in both experiments, but the magnitude of changes varied between diatom taxa. DFB additions resulted in reduced Fe quotas in the low-Fe incubation, since cells were presumably forced to use internal Fe stores to support growth. These data demonstrate significant plasticity in the abilities of phytoplankton to take advantage of changing micronutrient inputs. Quota data will be compared to transcript abundance data to ascertain mechanisms of Fe quota maintenance.

Geochemical behaviour of dissolved trace elements in a monsoon-dominated tropical river basin, Southwestern India.

PubMed

Gurumurthy, G P; Balakrishna, K; Tripti, M; Audry, Stéphane; Riotte, Jean; Braun, J J; Udaya Shankar, H N

2014-04-01

The study presents a 3-year time series data on dissolved trace elements and rare earth elements (REEs) in a monsoon-dominated river basin, the Nethravati River in tropical Southwestern India. The river basin lies on the metamorphic transition boundary which separates the Peninsular Gneiss and Southern Granulitic province belonging to Archean and Tertiary-Quaternary period (Western Dharwar Craton). The basin lithology is mainly composed of granite gneiss, charnockite and metasediment. This study highlights the importance of time series data for better estimation of metal fluxes and to understand the geochemical behaviour of metals in a river basin. The dissolved trace elements show seasonality in the river water metal concentrations forming two distinct groups of metals. First group is composed of heavy metals and minor elements that show higher concentrations during dry season and lesser concentrations during the monsoon season. Second group is composed of metals belonging to lanthanides and actinides with higher concentration in the monsoon and lower concentrations during the dry season. Although the metal concentration of both the groups appears to be controlled by the discharge, there are important biogeochemical processes affecting their concentration. This includes redox reactions (for Fe, Mn, As, Mo, Ba and Ce) and pH-mediated adsorption/desorption reactions (for Ni, Co, Cr, Cu and REEs). The abundance of Fe and Mn oxyhydroxides as a result of redox processes could be driving the geochemical redistribution of metals in the river water. There is a Ce anomaly (Ce/Ce*) at different time periods, both negative and positive, in case of dissolved phase, whereas there is positive anomaly in the particulate and bed sediments. The Ce anomaly correlates with the variations in the dissolved oxygen indicating the redistribution of Ce between particulate and dissolved phase under acidic to neutral pH and lower concentrations of dissolved organic carbon. Unlike other tropical and major world rivers, the effect of organic complexation on metal variability is negligible in the Nethravati River water.

Acidity and Alkalinity in mine drainage: Practical considerations

USGS Publications Warehouse

Cravotta, III, Charles A.; Kirby, Carl S.

2004-01-01

In this paper, we emphasize that the Standard Method hot peroxide treatment procedure for acidity determination (hot acidity) directly measures net acidity or net alkalinity, but that more than one water-quality measure can be useful as a measure of the severity of acid mine drainage. We demonstrate that the hot acidity is related to the pH, alkalinity, and dissolved concentrations of Fe, Mn, and Al in fresh mine drainage. We show that the hot acidity accurately indicates the potential for pH to decrease to acidic values after complete oxidation of Fe and Mn, and it indicates the excess alkalinity or that required for neutralization of the sample. We show that the hot acidity method gives consistent, interpretable results on fresh or aged samples. Regional data for mine-drainage quality in Pennsylvania indicated the pH of fresh samples was predominantly acidic (pH 2.5 to 4) or near neutral (pH 6 to 7); approximately 25 percent of the samples had intermediate pH values. This bimodal frequency distribution of pH was distinctive for fully oxidized samples; oxidized samples had acidic or near-neutral pH, only. Samples that had nearneutral pH after oxidation had negative hot acidity; samples that had acidic pH after oxidation had positive hot acidity. Samples with comparable pH values had variable hot acidities owing to variations in their alkalinities and dissolved Fe, Mn, and Al concentrations. The hot acidity was comparable to net acidity computed on the basis of initial pH and concentrations of Fe, Mn, and Al minus the initial alkalinity. Acidity computed from the pH and dissolved metals concentrations, assuming equivalents of 2 per mole of Fe and Mn and 3 per mole of Al, was comparable to that computed on the basis of aqueous species and FeII/FeIII. Despite changes in the pH, alkalinity, and metals concentrations, the hot acidities were comparable for fresh and aged samples. Thus, meaningful “net” acidity can be determined from a measured hot acidity or by calculation from the pH, alkalinity, and dissolved metals concentrations. Together, these water-quality data can be useful for evaluating the potential for toxicity, corrosion, or encrustation and can be helpful for determining the appropriate remediation. By demonstrating the measurements on fresh and aged samples, we hope to encourage (1) consistent use of the hot peroxide treatment procedure for acidity determination and (2) consistent reporting of negative acidity values.

The Organic Complexation of Iron in the Marine Environment: A Review

PubMed Central

Gledhill, Martha; Buck, Kristen N.

2012-01-01

Iron (Fe) is an essential micronutrient for marine organisms, and it is now well established that low Fe availability controls phytoplankton productivity, community structure, and ecosystem functioning in vast regions of the global ocean. The biogeochemical cycle of Fe involves complex interactions between lithogenic inputs (atmospheric, continental, or hydrothermal), dissolution, precipitation, scavenging, biological uptake, remineralization, and sedimentation processes. Each of these aspects of Fe biogeochemical cycling is likely influenced by organic Fe-binding ligands, which complex more than 99% of dissolved Fe. In this review we consider recent advances in our knowledge of Fe complexation in the marine environment and their implications for the biogeochemistry of Fe in the ocean. We also highlight the importance of constraining the dissolved Fe concentration value used in interpreting voltammetric titration data for the determination of Fe speciation. Within the published Fe speciation data, there appear to be important temporal and spatial variations in Fe-binding ligand concentrations and their conditional stability constants in the marine environment. Excess ligand concentrations, particularly in the truly soluble size fraction, seem to be consistently higher in the upper water column, and especially in Fe-limited, but productive, waters. Evidence is accumulating for an association of Fe with both small, well-defined ligands, such as siderophores, as well as with larger, macromolecular complexes like humic substances, exopolymeric substances, and transparent exopolymers. The diverse size spectrum and chemical nature of Fe ligand complexes corresponds to a change in kinetic inertness which will have a consequent impact on biological availability. However, much work is still to be done in coupling voltammetry, mass spectrometry techniques, and process studies to better characterize the nature and cycling of Fe-binding ligands in the marine environment. PMID:22403574

The influence of groundwater chemistry on arsenic concentrations and speciation in a quartz sand and gravel aquifer

USGS Publications Warehouse

Kent, D.B.; Fox, P.M.

2004-01-01

We examined the chemical reactions influencing dissolved concentrations, speciation, and transport of naturally occurring arsenic (As) in a shallow, sand and gravel aquifer with distinct geochemical zones resulting from land disposal of dilute sewage effluent. The principal geochemical zones were: (1) the uncontaminated zone above the sewage plume [350 ??M dissolved oxygen (DO), pH 5.9]; (2) the suboxic zone (5 ??M DO, pH 6.2, elevated concentrations of sewage-derived phosphate and nitrate); and (3) the anoxic zone [dissolved iron(II) 100-300 ??M, pH 6.5-6.9, elevated concentrations of sewage-derived phosphate]. Sediments are comprised of greater than 90% quartz but the surfaces of quartz and other mineral grains are coated with nanometer-size iron (Fe) and aluminum (Al) oxides and/or silicates, which control the adsorption properties of the sediments. Uncontaminated groundwater with added phosphate (620 ??M) was pumped into the uncontaminated zone while samples were collected 0.3 m above the injection point. Concentrations of As(V) increased from below detection (0.005 ??M) to a maximum of 0.07 ??M during breakthrough of phosphate at the sampling port; As(III) concentrations remained below detection. These results are consistent with the hypothesis that naturally occurring As(V) adsorbed to constituents of the coatings on grain surfaces was desorbed by phosphate in the injected groundwater. Also consistent with this hypothesis, vertical profiles of groundwater chemistry measured prior to the tracer test showed that dissolved As(V) concentrations increased along with dissolved phosphate from below detection in the uncontaminated zone to approximately 0.07 and 70 ??M, respectively, in the suboxic zone. Concentrations of As(III) were below detection in both zones. The anoxic zone had approximately 0.07 ??M As(V) but also had As(III) concentrations of 0.07-0.14 ??M, suggesting that release of As bound to sediment grains occurred by desorption by phosphate, reductive dissolution of Fe oxides, and reduction of As(V) to As(III), which adsorbs only weakly to the Fe-oxide-depleted material in the coatings. Results of reductive extractions of the sediments suggest that As associated with the coatings was relatively uniformly distributed at approximately 1 nmol/g of sediment (equivalent to 0.075 ppm As) and comprised 20%-50% of the total As in the sediments, determined from oxidative extractions. Quartz sand aquifers provide high-quality drinking water but can become contaminated when naturally occurring arsenic bound to Fe and Al oxides or silicates on sediment surfaces is released by desorption and dissolution of Fe oxides in response to changing chemical conditions. ?? 2004 American Institute of Physics.

Ferrihydrite dissolution by pyridine-2,6-bis(monothiocarboxylic acid) and hydrolysis products

NASA Astrophysics Data System (ADS)

Dhungana, Suraj; Anthony, Charles R.; Hersman, Larry E.

2007-12-01

Pyridine-2,6-bis(monothiocarboxylate) (pdtc), a metabolic product of microorganisms, including Pseudomonas putida and Pseudomonas stutzeri was investigated for its ability of dissolve Fe(III)(hydr)oxides at pH 7.5. Concentration dependent dissolution of ferrihydrite under anaerobic environment showed saturation of the dissolution rate at the higher concentration of pdtc. The surface controlled ferrihydrite dissolution rate was determined to be 1.2 × 10 -6 mol m -2 h -1. Anaerobic dissolution of ferrihydrite by pyridine-2,6-dicarboxylic acid or dipicolinic acid (dpa), a hydrolysis product of pdtc, was investigated to study the mechanism(s) involved in the pdtc facilitated ferrihydrite dissolution. These studies suggest that pdtc dissolved ferrihydrite using a reduction step, where dpa chelates the Fe reduced by a second hydrolysis product, H 2S. Dpa facilitated dissolution of ferrihydrite showed very small increase in the Fe dissolution when the concentration of external reductant, ascorbate, was doubled, suggesting the surface dynamics being dominated by the interactions between dpa and ferrihydrite. Greater than stoichiometric amounts of Fe were mobilized during dpa dissolution of ferrihydrite assisted by ascorbate and cysteine. This is attributed to the catalytic dissolution of Fe(III)(hydr)oxides by the in situ generated Fe(II) in the presence of a complex former, dpa.

Monitoring, field experiments, and geochemical modeling of Fe(II) oxidation kinetics in a stream dominated by net-alkaline coal-mine drainage, Pennsylvania, USA

USGS Publications Warehouse

Cravotta, Charles A.

2015-01-01

Watershed-scale monitoring, field aeration experiments, and geochemical equilibrium and kinetic modeling were conducted to evaluate interdependent changes in pH, dissolved CO2, O2, and Fe(II) concentrations that typically take place downstream of net-alkaline, circumneutral coal-mine drainage (CMD) outfalls and during aerobic treatment of such CMD. The kinetic modeling approach, using PHREEQC, accurately simulates observed variations in pH, Fe(II) oxidation, alkalinity consumption, and associated dissolved gas concentrations during transport downstream of the CMD outfalls (natural attenuation) and during 6-h batch aeration tests on the CMD using bubble diffusers (enhanced attenuation). The batch aeration experiments demonstrated that aeration promoted CO2 outgassing, thereby increasing pH and the rate of Fe(II) oxidation. The rate of Fe(II) oxidation was accurately estimated by the abiotic homogeneous oxidation rate law −d[Fe(II)]/dt = k1·[O2]·[H+]−2·[Fe(II)] that indicates an increase in pH by 1 unit at pH 5–8 and at constant dissolved O2 (DO) concentration results in a 100-fold increase in the rate of Fe(II) oxidation. Adjusting for sample temperature, a narrow range of values for the apparent homogeneous Fe(II) oxidation rate constant (k1′) of 0.5–1.7 times the reference value of k1 = 3 × 10−12 mol/L/min (for pH 5–8 and 20 °C), reported by Stumm and Morgan (1996), was indicated by the calibrated models for the 5-km stream reach below the CMD outfalls and the aerated CMD. The rates of CO2 outgassing and O2ingassing in the model were estimated with first-order asymptotic functions, whereby the driving force is the gradient of the dissolved gas concentration relative to equilibrium with the ambient atmosphere. Although the progressive increase in DO concentration to saturation could be accurately modeled as a kinetic function for the conditions evaluated, the simulation of DO as an instantaneous equilibrium process did not affect the model results for Fe(II) or pH. In contrast, the model results for pH and Fe(II) were sensitive to the CO2 mass transfer rate constant (kL,CO2a). The value of kL,CO2a estimated for the stream (0.010 min−1) was within the range for the batch aeration experiments (0–0.033 min−1). These results indicate that the abiotic homogeneous Fe(II) oxidation rate law, with adjustments for variations in temperature and CO2 outgassing rate, may be applied to predict changes in aqueous iron and pH for net-alkaline, ferruginous waters within a stream (natural conditions) or a CMD treatment system (engineered conditions).

Geochemical evolution of acidic ground water at a reclaimed surface coal mine in western Pennsylvania

USGS Publications Warehouse

Cravotta,, Charles A.

1991-01-01

Concentrations of dissolved sulfate and acidity in ground water increase downflow in mine spoil and underlying bedrock at a reclaimed surface coal mine in the bituminous field of western Pennsylvania. Elevated dissolved sulfate and negligible oxygen in ground water from bedrock about 100 feet below the water table suggest that pyritic sulfur is oxidized below the water table, in a system closed to oxygen. Geochemical models for the oxidation of pyrite (FeS2) and production of sulfate (SO42-) and acid (H+) are presented to explain the potential role of oxygen (O2) and ferric iron (Fe3+) as oxidants. Oxidation of pyrite by O2 and Fe3+ can occur under oxic conditions above the water table, whereas oxidation by Fe3+ also can occur under anoxic conditions below the water table. The hydrated ferric-sulfate minerals roemerite [Fe2+Fe43+(SO4)4·14H2O], copiapite [Fe2+Fe43+(SO4)6(OH)2·20H20], and coquimbite [Fe2(SO4)3·9H2O] were identified with FeS2 in coal samples, and form on the oxidizing surface of pyrite in an oxic system above the water table. These soluble ferric-sulfate 11 salts11 can dissolve with recharge waters or a rising water table releasing Fe3+, SO42-. and H+, which can be transported along closed-system ground-water flow paths to pyrite reaction sites where O2 may be absent. The Fe3+ transported to these sites can oxidize pyritic sulfur. The computer programs WATEQ4F and NEWBAL were used to compute chemical speciation and mass transfer, respectively, considering mineral dissolution and precipitation reactions plus mixing of waters from different upflow zones. Alternative mass-balance models indicate that (a) extremely large quantities of O2, over 100 times its aqueous solubility, can generate the observed concentrations of dissolved SO42- from FeS2, or (b) under anoxic conditions, Fe3+ from dissolved ferric-sulfate minerals can oxidize FeS2 along closed-system ground-water flow paths. In a system open to O2, such as in the unsaturated zone, the aqueous solubility of O2 is not limiting, and oxidation of pyrite by O2 and Fe3+ accounts for most SO42- and Fe2+ observed in acidic ground water. However, in a system closed to O2, such as in the saturated zone, O2 solubility is limiting; hence, ferric oxidation of pyrite is a reasonable explanation for the observed elevated SO42- with increasing depth below the water table.

Removal of H 2S via an iron catalytic cycle and iron sulfide precipitation in the water column of dead end tributaries

NASA Astrophysics Data System (ADS)

Ma, Shufen; Noble, Abigail; Butcher, Derek; Trouwborst, Robert E.; Luther, George W., III

2006-11-01

The oxidation and precipitation of H 2S were investigated in Torquay Canal and Bald Eagle Creek, two tributaries of northern Rehoboth Bay, one of the Delaware Inland Bays. These man-made dead end canals develop seasonal anoxia and have been the site of past fish kills and harmful algal blooms. The canals have multiple holes over 5.5 m deep compared to an average low tide depth of 2 m. In situ determination for dissolved O 2, H 2S and other Fe and S redox species were conducted with a solid-state Au/Hg microelectrode in 2003 and 2004. Laboratory analyses of discrete samples were also performed to measure dissolved and particulate Fe, Mn, and S 8 to follow the seasonal dynamics of O, S, Fe and Mn redox species. Our results indicate that the water in the holes becomes stratified with O 2 decreasing with depth and H 2S increasing with depth. Dissolved Fe was as high as 30 μM whereas dissolved Mn was only 0.2 μM in the water column, indicating that Fe is the dominant metal involved in S redox cycling and precipitation. In surface oxic waters, the dominant form of Fe was particulate Fe(III) (oxy)hydroxides. When seasonal anoxia developed, Fe(III) (oxy)hydroxides were reduced by H 2S to Fe(II) at the oxic-anoxic interface. The Fe(II) reduced from particulate Fe can be re-oxidized to Fe(III) by O 2 above and at the interface to form a catalytic cycle to oxidize H 2S. Elemental S is the predominant oxidation product and was as high as 30 μM level (as S 0) at the interface. When the system was stable, the Fe catalytic cycle prevented H 2S from being released into surface waters during seasonal anoxia. However, when storms came, the water column was overturned and H 2S was released to the surface water. The reaction rates for the Fe catalytic cycle are not fast enough and the concentration of Fe was not high enough to regulate the high concentration of H 2S in surface waters during storm and mixing events.

Dissolved Organic Matter Quality in a Shallow Aquifer of Bangladesh: Implications for Arsenic Mobility.

PubMed

Mladenov, Natalie; Zheng, Yan; Simone, Bailey; Bilinski, Theresa M; McKnight, Diane M; Nemergut, Diana; Radloff, Kathleen A; Rahman, M Moshiur; Ahmed, Kazi Matin

2015-09-15

In some high arsenic (As) groundwater systems, correlations are observed between dissolved organic matter (DOM) and As concentrations, but in other systems, such relationships are absent. The role of labile DOM as the main driver of microbial reductive dissolution is not sufficient to explain the variation in DOM-As relationships. Other processes that may also influence As mobility include complexation of As by dissolved humic substances, and competitive sorption and electron shuttling reactions mediated by humics. To evaluate such humic DOM influences, we characterized the optical properties of filtered surface water (n = 10) and groundwater (n = 24) samples spanning an age gradient in Araihazar, Bangladesh. Further, we analyzed large volume fulvic acid (FA) isolates (n = 6) for optical properties, C and N content, and (13)C NMR spectroscopic distribution. Old groundwater (>30 years old) contained primarily sediment-derived DOM and had significantly higher (p < 0.001) dissolved As concentration than groundwater that was younger than 5 years old. Younger groundwater had DOM spectroscopic signatures similar to surface water DOM and characteristic of a sewage pollution influence. Associations between dissolved As, iron (Fe), and FA concentration and fluorescence properties of isolated FA in this field study suggest that aromatic, terrestrially derived FAs promote As-Fe-FA complexation reactions that may enhance As mobility.

Porewater inputs drive Fe redox cycling in the water column of a temperate mangrove wetland

NASA Astrophysics Data System (ADS)

Holloway, Ceylena J.; Santos, Isaac R.; Rose, Andrew L.

2018-07-01

Iron is a vital micronutrient within coastal marine ecosystems, playing an integral role in the scale and dynamics of primary production and carbon cycling in the world's oceans. We investigated the relative importance of in situ Fe(II) production from photochemical, microbial and thermal Fe reduction in the surface water column as well as advective porewater inputs in a temperate saline wetland in Australia containing mangrove and saltmarsh vegetation. The diel average concentration of Fe(II) (0.63 ± 0.21 μM, accounting for >70% of the total dissolved Fe present in surface water) was much higher than commonly reported in oxygenated marine waters despite high dissolved oxygen concentrations (81-112% saturation), pH (7.7-7.8) and salinity (33-36) that favor Fe oxidation. In situ production of Fe(II) in the surface water column was primarily driven by microbial processes rather than photochemical and thermal reduction, with a maximum production rate of 4.9 × 10-3 nM s-1. Advective porewater Fe(II) inputs to the wetland averaged over a diel cycle (3.0 × 10-1 nM s-1) were an order of magnitude greater than the combined Fe(II) production rate from autochthonous water column processes (1.0 × 10-2 nM s-1). A bottom up model based on the estimated individual fluxes was used to explain the high Fe(II) concentrations measured during a 24 h time series experiment. Combined, different lines of evidence suggest that advective porewater exchange provides significant quantities of Fe(II) to the estuarine wetland.

Importance of Ekman transport and gyre circulation change on seasonal variation of surface dissolved iron in the western subarctic North Pacific

NASA Astrophysics Data System (ADS)

Nakanowatari, Takuya; Nakamura, Tomohiro; Uchimoto, Keisuke; Nishioka, Jun; Mitsudera, Humio; Wakatsuchi, Masaaki

2017-05-01

Iron (Fe) is an essential nutrient for marine phytoplankton and it constitutes an important element in the marine carbon cycle in the ocean. This study examined the mechanisms controlling seasonal variation of dissolved Fe (dFe) in the western subarctic North Pacific (WSNP), using an ocean general circulation model coupled with a simple biogeochemical model incorporating a dFe cycle fed by two major sources (atmospheric dust and continental shelf sediment). The model reproduced the seasonal cycle of observed concentrations of dFe and macronutrients at the surface in the Oyashio region with maxima in winter (February-March) and minima in summer (July-September), although the simulated seasonal amplitudes are a half of the observed values. Analysis of the mixed-layer dFe budget indicated that both local vertical entrainment and lateral advection are primary contributors to the wintertime increase in dFe concentration. In early winter, strengthened northwesterly winds excite southward Ekman transport and Ekman upwelling over the western subarctic gyre, transporting dFe-rich water southward. In mid to late winter, the southward western boundary current of the subarctic gyre and the outflow from the Sea of Okhotsk also bring dFe-rich water to the Oyashio region. The contribution of atmospheric dust to the dFe budget is several times smaller than these ocean transport processes in winter. These results suggest that the westerly wind-induced Ekman transport and gyre circulation systematically influence the seasonal cycle of WSNP surface dFe concentration.

Seasonal and spatial variabilities in northern Gulf of Alaska surface water iron concentrations driven by shelf sediment resuspension, glacial meltwater, a Yakutat eddy, and dust

NASA Astrophysics Data System (ADS)

Crusius, John; Schroth, Andrew W.; Resing, Joseph A.; Cullen, Jay; Campbell, Robert W.

2017-06-01

Phytoplankton growth in the Gulf of Alaska (GoA) is limited by iron (Fe), yet Fe sources are poorly constrained. We examine the temporal and spatial distributions of Fe, and its sources in the GoA, based on data from three cruises carried out in 2010 from the Copper River (AK) mouth to beyond the shelf break. April data are the first to describe late winter Fe behavior before surface water nitrate depletion began. Sediment resuspension during winter and spring storms generated high "total dissolvable Fe" (TDFe) concentrations of 1000 nmol kg-1 along the entire continental shelf, which decreased beyond the shelf break. In July, high TDFe concentrations were similar on the shelf, but more spatially variable, and driven by low-salinity glacial meltwater. Conversely, dissolved Fe (DFe) concentrations in surface waters were far lower and more seasonally consistent, ranging from 4 nmol kg-1 in nearshore waters to 0.6-1.5 nmol kg-1 seaward of the shelf break during April and July, despite dramatic depletion of nitrate over that period. The reasonably constant DFe concentrations are likely maintained during the year across the shelf by complexation by strong organic ligands, coupled with ample supply of labile particulate Fe. The April DFe data can be simulated using a simple numerical model that assumes a DFe flux from shelf sediments, horizontal transport by eddy diffusion, and removal by scavenging. Given how global change is altering many processes impacting the Fe cycle, additional studies are needed to examine controls on DFe in the Gulf of Alaska.

Strontium and Trace Metals in the Mississippi River Mixing Zone

NASA Astrophysics Data System (ADS)

Xu, Y.; Marcantonio, F.

2001-12-01

Strontium is generally believed to be a conservative element, i.e., it is assumed that dissolved Sr moves directly from rivers through estuaries to the ocean. More recently, however, detailed sampling of rivers suggests a weak non-conservative behavior for Sr. Here, we present dissolved and suspended load Sr and trace metal data for samples retrieved along salinity transects in the estuarine mixing zone of the Mississippi River. Our cruises took place during times representing high, falling, and low Mississippi River discharge. Sr concentration and isotopic composition were analyzed for both dissolved particulate loads. Selected particle-reactive or redox-sensitive trace metals (Mn, Fe, U, V, Mo, Ti, and Pb) were analyzed simultaneously. In the dissolved load, Sr showed conservative behavior in both high- and low- discharge periods. Non-conservative behavior of Sr predominated during falling discharge in the summer. Significant positive correlations were found between Sr, Mo and Ti. U and V distributions were found to be essentially controlled by mixing of river water and seawater, but with significantly lower riverine concentrations during high-flow stage. Particulate element concentrations can be quite variable and heterogeneous. In this study, strong correlations were found between particulate Mn (and Fe) concentrations and particulate concentrations of Ti, U, V, and Pb. No such correlations with Mn (or Fe) were found for particulate Sr and Mo. There is a vast hypoxic zone along the coast of Louisiana in the Gulf of Mexico that exists during the summer months. Based on the Sr isotope systematics and the relationships between Sr and trace metals, we believe that this eutrophication may contribute to the non-conservative behaviors of Sr and other trace metals. We discuss the potential implications of this hypothesis on the Sr mass balance of present-day and past seawater.

Role of Dissolved Organic Matter and Geochemical Controls on Arsenic Cycling from Sediments to Groundwater along the Meghna River, Bangladesh: Tracking possible links to permeable natural reactive barrier

NASA Astrophysics Data System (ADS)

Datta, S.; Berube, M.; Knappett, P.; Kulkarni, H. V.; Vega, M.; Jewell, K.; Myers, K.

2017-12-01

Elevated levels of dissolved arsenic (As), iron (Fe) and manganese (Mn) are seen in the shallow groundwaters of southeast Bangladesh on the Ganges Brahmaputra Meghna River delta. This study takes a multi disciplinary approach to understand the extent of the natural reactive barrier (NRB) along the Meghna River and evaluate the role of the NRB in As sequestration and release in groundwater aquifers. Shallow sediment cores, and groundwater and river water samples were collected from the east and west banks of the Meghna. Groundwater and river water samples were tested for FeT, MnT, and AsT concentrations. Fluorescence spectroscopic characterization of groundwater dissolved organic matter (DOM) provided insight into the hydro geochemical reactions active in the groundwater and the hyporheic zones. Eight sediment cores of 1.5 m depth were collected 10 m away from the edge of the river. Vertical solid phase concentration profiles of Fe, Mn and As were measured via 1.2 M HCl digestion which revealed solid phase As accumulation along the riverbanks up to concentrations of 1500 mg/kg As. Microbial interactions with DOM prompts the reduction of Fe3+ to Fe2+, causing As to mobilize into groundwater and humic-like DOM present in the groundwater may catalyze this process. The extent to which microbially mediated release of As occurs is limited by labile dissolved organic carbon (DOC) availability. Aqueous geochemical results showed the highest dissolved As concentrations in shallow wells (<30 m depth), where organic matter was fresh, humic-like, and aromatic. Based on fluorescence characterization, shallow groundwater was found to contain microbial and terrestrial derived DOC, and decomposed, humified and aromatic DOM. Deeper aquifers had a significantly larger microbial OM signature than the shallower aquifers and was less aromatic, decomposed and humified. The results from this study illustrate the potential for humic substances to contribute to As cycling and quantify the extent of As accumulation in the sediments and groundwater along a 1 km stretch of the Meghna. These findings contribute to the overall understanding of geochemical processes involved in As release into groundwaters from sediments within a fluvial deltaic environment and close proximity to a possible permeable natural reactive barrier.

Passive aerobic treatment of net-alkaline, iron-laden drainage from a flooded underground anthracite mine, Pennsylvania, USA

USGS Publications Warehouse

Cravotta, C.A.

2007-01-01

This report evaluates the results of a continuous 4.5-day laboratory aeration experiment and the first year of passive, aerobic treatment of abandoned mine drainage (AMD) from a typical flooded underground anthracite mine in eastern Pennsylvania, USA. During 1991-2006, the AMD source, locally known as the Otto Discharge, had flows from 20 to 270 L/s (median 92 L/s) and water quality that was consistently suboxic (median 0.9 mg/L O2) and circumneutral (pH ??? 6.0; net alkalinity >10) with moderate concentrations of dissolved iron and manganese and low concentrations of dissolved aluminum (medians of 11, 2.2, and <0.2 mg/L, respectively). In 2001, the laboratory aeration experiment demonstrated rapid oxidation of ferrous iron (Fe 2+) without supplemental alkalinity; the initial Fe2+ concentration of 16.4 mg/L decreased to less than 0.5 mg/L within 24 h; pH values increased rapidly from 5.8 to 7.2, ultimately attaining a steady-state value of 7.5. The increased pH coincided with a rapid decrease in the partial pressure of carbon dioxide (PCO2) from an initial value of 10 -1.1atm to a steady-state value of 10-3.1atm. From these results, a staged aerobic treatment system was conceptualized consisting of a 2 m deep pond with innovative aeration and recirculation to promote rapid oxidation of Fe2+, two 0.3 m deep wetlands to facilitate iron solids removal, and a supplemental oxic limestone drain for dissolved manganese and trace-metal removal. The system was constructed, but without the aeration mechanism, and began operation in June 2005. During the first 12 months of operation, estimated detention times in the treatment system ranged from 9 to 38 h. However, in contrast with 80-100% removal of Fe2+ over similar elapsed times during the laboratory aeration experiment, the treatment system typically removed less than 35% of the influent Fe2+. Although concentrations of dissolved CO2 decreased progressively within the treatment system, the PCO2 values for treated effluent remained elevated (10-2.4 to 10-1.7atm). The elevated PCO 2 maintained the pH within the system at values less than 7 and hence slowed the rate of Fe2+ oxidation compared to the aeration experiment. Kinetic models of Fe2+ oxidation that consider effects of pH and dissolved O2 were incorporated in the geochemical computer program PHREEQC to evaluate the effects of detention time, pH, and other variables on Fe2+ oxidation and removal rates. These models and the laboratory aeration experiment indicate that performance of this and other aerobic wetlands for treatment of net-alkaline AMD could be improved by aggressive, continuous aeration in the initial stage to decrease PCO 2, increase pH, and accelerate Fe2+ oxidation. ?? 2007 Springer-Verlag.

Photochemical Reactivity of Dissolved Organic Matter in Boreal Lakes

NASA Astrophysics Data System (ADS)

Gu, Y.; Vuorio, K.; Tiirola, M.; Perämäki, S.; Vahatalo, A.

2016-12-01

Boreal lakes are rich in dissolved organic matter (DOM) that terrestrially derived from forest soil and wetland, yet little is known about potential for photochemical transformation of aquatic DOM in boreal lakes. Transformation of chromophoric dissolved organic matter (CDOM) can decrease water color and enhance microbial mineralization, affecting primary production and respiration, which both affect the CO2 balance of the lakes. We used laboratory solar radiation exposure experiments with lake water samples collected from 54 lakes located in Finland and Sweden, representing different catchment composition and watershed location to assess photochemical reactivity of DOM. The pH of water samples ranged from 5.4 to 8.3, and the concentrations of dissolved iron (Fe) were between < 0.06 and 22 μmol L-1. The filtered water samples received simulated solar radiation corresponding to a daily dose of sunlight, and photomineralization of dissolved organic carbon (DOC) to dissolved inorganic carbon (DIC) was measured for determination of spectral apparent quantum yields (AQY). During irradiation, photobleaching decreased the absorption coefficients of CDOM at 330 nm between 4.9 and 79 m-1 by 0.5 to 11 m-1. Irradiation generated DIC from 2.8 to 79 μmol C L-1. The AQY at 330 nm ranged between 31 and 273 ×10-6 mol C mol photons-1 h-1, which was correlated positively with concentration of dissolved Fe, and negatively with pH. Further statistical analyze indicated that the interaction between pH and Fe may explain much of the photochemical reactivity of DOM in the examined lakes, and land cover concerns main catchment areas also can have impact on the photoreaction process. This study may suggest how environmental conditions regulate DOM photomineralization in boreal lakes.

Seasonality of major redox constituents in a shallow subterranean estuary

NASA Astrophysics Data System (ADS)

O'Connor, Alison E.; Krask, Julie L.; Canuel, Elizabeth A.; Beck, Aaron J.

2018-03-01

The subterranean estuary (STE), the subsurface mixing zone of outflowing fresh groundwater and infiltrating seawater, is an area of extensive geochemical reactions that determine the composition of groundwater that flows into coastal environments. This study examined the porewater composition of a shallow STE (<5 m depth) in Gloucester Point, VA (USA) over two years to determine seasonal variations in dissolved organic carbon (DOC) and the reduced metabolites Fe, Mn, and sulfide. An additional aim of this study was to investigate the relative importance of salinity gradients (which have great geochemical influence in surface estuaries) versus redox gradients on STE geochemistry. Two freshwater endmembers were identified, between which redox potential and composition varied with depth-a shallow freshwater endmember was oxidizing and high in DOC, whereas a deep freshwater endmember was reducing, lower in DOC, and high in sulfide. Results showed that dissolved Fe, Mn, and sulfide varied along a redox gradient distinct from the salinity gradient, and that three-endmember mixing was required to quantify non-conservative chemical addition/removal in the STE. In addition to salinity, humic carbon was used as a quasi-conservative tracer to quantify mixing according to a three-endmember model. The vertical distributions of DOC and reduced metabolites remained approximately constant over time, but concentrations varied with season. Dissolved organic carbon concentrations were greatest in the summer, and shallow meteoric groundwater supplied the majority of DOC to the STE. In summer, there was additional evidence for shallow non-conservative addition of DOC. Dissolved Fe and Mn were highest in a subsurface plume through the middle of the STE (100-140 cm below sediment surface at the high tide line) which was characterized by higher concentrations and greater non-conservative addition in the winter. In contrast, sulfide was higher in summer at depths within the Fe and Mn plume (100-140 cm). We attribute the contrasting seasonal patterns of dissolved Fe, Mn, and sulfide to differences in microbial response to temperature changes and organic matter availability, and to competition at the ferrous-sulfidic transition zone between dissimilatory metal reduction and sulfate reduction, leading to sulfate/sulfur reducing bacteria (SRB) being more active in summer and metal reducers being more active in winter. Throughout the STE, seasonal temperature and DOC variations determined the spatial distribution and geochemical cycling of Fe, Mn, and sulfur.

Decoupling of As and Fe release to Bangladesh groundwater under reducing conditions. Part I: Evidence from sediment profiles

NASA Astrophysics Data System (ADS)

Horneman, A.; van Geen, A.; Kent, D. V.; Mathe, P. E.; Zheng, Y.; Dhar, R. K.; O'Connell, S.; Hoque, M. A.; Aziz, Z.; Shamsudduha, M.; Seddique, A. A.; Ahmed, K. M.

2004-09-01

This study reexamines the notion that extensive As mobilization in anoxic groundwater of Bangladesh is intimately linked to the dissolution of Fe oxyhydroxides on the basis of analyses performed on a suite of freshly collected samples of aquifer material. Detailed sediment profiles extending to 40 to 70 m depth below the surface were obtained at six sites where local groundwater As concentrations were known to span a wide range. The sediment properties that were measured include (1) the proportion of Fe(II) in the Fe fraction leached in hot 1.2 N HCl, (2) diffuse spectral reflectance, and (3) magnetic susceptibility. In parallel with local concentrations of dissolved As ranging from <5 to 600 μg/L, Fe(II)/Fe ratios in shallow (gray) Holocene sands tended to gradually increase with depth from values of 0.3 to 0.5 to up to 0.9. In deeper (orange) aquifers of presumed Pleistocene age that were separated from shallow sands by a clay layer and contained <5 μg/L dissolved As, leachable Fe(II)/Fe ratios averaged ˜0.2. There was no consistent relation between sediment Fe(II)/Fe and dissolved Fe concentrations in groundwater in nearby wells. The reflectance measurements indicate a systematic linear relation (R 2 of 0.66; n = 151) between the first derivative transform of the reflectance at 520 nm and Fe(II)/Fe. The magnetic susceptibility of the shallow aquifer sands ranged from 200 to 3600 (x 10 -9 m 3/kg SI) and was linearly related (R 2 of 0.75; n = 29) to the concentrations of minerals that could be magnetically separated (0.03 to 0.79% dry weight). No systematic depth trends in magnetic susceptibility were observed within the shallow sands, although the susceptibility of deeper low-As aquifers was low (up to ˜200 × 10 -9 m 3/kg SI). This set of observations, complemented by incubation results described in a companion paper by van Geen et al. (this volume), suggests that the release of As is linked to the transformation of predominantly Fe (III) oxyhydroxide coatings on sand particles to Fe(II) or mixed Fe(II/III) solid phases with a flatter reflectance spectrum such as siderite, vivianite, or magnetite, without necessarily resulting in the release of Fe to groundwater. The very low As/Fe ratio of magnetically separated minerals compared to the As/Fe of bulk acid leachate (2 vs. 40 10 -6, respectively) suggests that such a transformation could be accompanied by a significant redistribution of As to a mobilizable phase on the surface of aquifer particles.

Inhibition of bacterial oxidation of ferrous iron by lead nitrate in sulfate-rich systems

USGS Publications Warehouse

Wang, Hongmei; Gong, Linfeng; Cravotta,, Charles A.; Yang, Xiaofen; Tuovinen, Olli H.; Dong, Hailiang; Fu, Xiang

2013-01-01

Inhibition of bacterial oxidation of ferrous iron (Fe(II)) by Pb(NO3)2 was investigated with a mixed culture of Acidithiobacillus ferrooxidans. The culture was incubated at 30 °C in ferrous-sulfate medium amended with 0–24.2 mM Pb(II) added as Pb(NO3)2. Anglesite (PbSO4) precipitated immediately upon Pb addition and was the only solid phase detected in the abiotic controls. Both anglesite and jarosite (KFe3(SO4)2(OH)6) were detected in inoculated cultures. Precipitation of anglesite maintained dissolved Pb concentrations at 16.9–17.6 μM regardless of the concentrations of Pb(NO3)2 added. Fe(II) oxidation was suppressed by 24.2 mM Pb(NO3)2 addition even when anglesite was removed before inoculation. Experiments with 0–48 mM KNO3 demonstrated that bacterial Fe(II) oxidation decreased as nitrate concentration increased. Therefore, inhibition of Fe(II) oxidation at 24.2 mM Pb(NO3)2 addition resulted from nitrate toxicity instead of Pb addition. Geochemical modeling that considered the initial precipitation of anglesite to equilibrium followed by progressive oxidation of Fe(II) and the precipitation of jarosite and an amorphous iron hydroxide phase, without allowing plumbojarosite to precipitate were consistent with the experimental time-series data on Fe(II) oxidation under biotic conditions. Anglesite precipitation in mine tailings and other sulfate-rich systems maintains dissolved Pb concentrations below the toxicity threshold of A. ferrooxidans.

An experimental study of basaltic glass-H2O-CO2 interaction at 22 and 50 ° C: Implications for subsurface storage of CO2

NASA Astrophysics Data System (ADS)

Galeczka, Iwona; Wolff-Boenisch, Domenik; Oelkers, Eric H.; Gislason, Sigurdur R.

2014-05-01

A novel high pressure column flow reactor (HPCFR) was used to investigate the evolution of fluid chemistry along a 2.3 meter flow path during 37-104 days of pure water- and CO2-charged water- (0.3 M CO2(aq)) basaltic glass interaction experiments at 22 and 50 ° C. The scale of the HPCFR, the ability to sample a reactive fluid at discrete spatial intervals under pressure and the possibility to measure the dissolved inorganic carbon and pH in situ all render the HPCFR unique in comparison with other reactors constructed for studies of CO2-charged water-rock interaction. During the pure water-basaltic glass interaction experiment, the pH of the injected water evolved rapidly from 6.7 to 9-9.5 and most of the dissolved iron was consumed by secondary mineral formation, similar to natural basaltic groundwater systems. In contrast to natural systems, however, the dissolved aluminium concentration remained relatively high along the entire flow path. The reactive fluid was undersaturated with respect to basaltic glass and carbonate minerals, but supersaturated with respect to zeolites, clays, and Fe hydroxides. Basaltic glass dissolution in the CO2-charged water was closer to stoichiometry than in pure water. The mobility of metals increased significantly in the reactive fluid and the concentration of some metals, including Mn, Fe, Cr, Al, and As exceeded the WHO (World Health Organisation) allowable drinking water limits. Iron was mobile and the aqueous Fe2+/Fe3+ ratio increased along the flow path. Basaltic glass dissolution in the CO2-charged water did not overcome the pH buffer capacity of the fluid. The pH rose only from an initial pH of 3.4 to 4.5 along the first 18.5 cm of the column, then remained constant during the remaining 2.1 meters of the flow path. Increasing the temperature of the CO2-charged fluid from 22 to 50 ° C increased the relative amount of dissolved divalent iron along the flow path. After a significant initial increase along the first metre of the column, the dissolved aluminium concentration decreased consistent with its incorporation into secondary minerals. The dissolved chromium concentration evolution mimicked that of Al at 50 ° C, suggesting substitution of trivalent Cr for Al in secondary phases. According to PHREEQC calculations, the CO2-charged fluid was always undersaturated with respect to carbonate minerals within the column, but supersaturated with respect to clays and Fe hydroxides at 22 ° C and with respect to clays and Al hydroxides at 50 ° C. Substantial differences were found between modelled and measured dissolved element concentrations in the fluids during the experiments. These differences underscore the need to improve computational models before they can be used to predict with confidence the fate and consequences of carbon dioxide injected into the subsurface.

Evolution of the chemistry of Fe bearing waters during CO2 degassing

USGS Publications Warehouse

Geroni, J.N.; Cravotta, C.A.; Sapsford, D.J.

2012-01-01

The rates of Fe(II) oxidation and precipitation from groundwater are highly pH dependent. Elevated levels of dissolved CO2 can depress pH and cause difficulty in removing dissolved Fe and associated metals during treatment of ferruginous water. This paper demonstrates interdependent changes in pH, dissolved inorganic C species, and Fe(II) oxidation rates that occur as a result of the removal (degassing) of CO2 during aeration of waters discharged from abandoned coal mines. The results of field monitoring of aeration cascades at a treatment facility as well as batchwise aeration experiments conducted using net alkaline and net acidic waters in the UK are combined with geochemical modelling to demonstrate the spatial and temporal evolution of the discharge water chemistry. The aeration cascades removed approximately 67% of the dissolved CO2 initially present but varying the design did not affect the concentration of Fe(II) leaving the treatment ponds. Continued removal of the residual CO2 by mechanical aeration increased pH by as much as 2 units and resulted in large increases in the rates of Fe(II) oxidation and precipitation. Effective exsolution of CO2 led to a reduction in the required lime dose for removal of remaining Fe(II), a very important factor with regard to increasing the sustainability of treatment practices. An important ancillary finding for passive treatment is that varying the design of the cascades had little impact on the rate of CO2 removal at the flow rates measured.

Evaluating remedial alternatives for an acid mine drainage stream: Application of a reactive transport model

USGS Publications Warehouse

Runkel, R.L.; Kimball, B.A.

2002-01-01

A reactive transport model based on one-dimensional transport and equilibrium chemistry is applied to synoptic data from an acid mine drainage stream. Model inputs include streamflow estimates based on tracer dilution, inflow chemistry based on synoptic sampling, and equilibrium constants describing acid/base, complexation, precipitation/dissolution, and sorption reactions. The dominant features of observed spatial profiles in pH and metal concentration are reproduced along the 3.5-km study reach by simulating the precipitation of Fe(III) and Al solid phases and the sorption of Cu, As, and Pb onto freshly precipitated iron-(III) oxides. Given this quantitative description of existing conditions, additional simulations are conducted to estimate the streamwater quality that could result from two hypothetical remediation plans. Both remediation plans involve the addition of CaCO3 to raise the pH of a small, acidic inflow from ???2.4 to ???7.0. This pH increase results in a reduced metal load that is routed downstream by the reactive transport model, thereby providing an estimate of post-remediation water quality. The first remediation plan assumes a closed system wherein inflow Fe(II) is not oxidized by the treatment system; under the second remediation plan, an open system is assumed, and Fe(II) is oxidized within the treatment system. Both plans increase instream pH and substantially reduce total and dissolved concentrations of Al, As, Cu, and Fe(II+III) at the terminus of the study reach. Dissolved Pb concentrations are reduced by ???18% under the first remediation plan due to sorption onto iron-(III) oxides within the treatment system and stream channel. In contrast, iron(III) oxides are limiting under the second remediation plan, and removal of dissolved Pb occurs primarily within the treatment system. This limitation results in an increase in dissolved Pb concentrations over existing conditions as additional downstream sources of Pb are not attenuated by sorption.

Iron oxidation kinetics and phosphate immobilization along the flow-path from groundwater into surface water

NASA Astrophysics Data System (ADS)

van der Grift, B.; Rozemeijer, J. C.; Griffioen, J.; van der Velde, Y.

2014-06-01

The retention of phosphorus in surface waters though co-precipitation of phosphate with Fe-oxyhydroxides during exfiltration of anaerobic Fe(II) rich groundwater is not well understood. We developed an experimental field set-up to study Fe(II) oxidation and P immobilization along the flow-path from groundwater to surface water in an agricultural experimental catchment of a small lowland river. We physically separated tube drain effluent from groundwater discharge before it entered a ditch in an agricultural field. Through continuous discharge measurements and weekly water quality sampling of groundwater, tube drain water, exfiltrated groundwater, and ditch water, we investigated Fe(II) oxidation kinetics and P immobilization processes. The oxidation rate inferred from our field measurements closely agreed with the general rate law for abiotic oxidation of Fe(II) by O2. Seasonal changes in climatic conditions affected the Fe(II) oxidation process. Lower pH and lower temperatures in winter (compared to summer) resulted in low Fe oxidation rates. After exfiltration to the surface water, it took a couple of days to more than one week before complete oxidation of Fe(II) is reached. In summer time, Fe oxidation rates were much higher. The Fe concentrations in the exfiltrated groundwater were low, indicating that dissolved Fe(II) is completely oxidized prior to inflow into a ditch. While the Fe oxidation rates reduce drastically from summer to winter, P concentrations remained high in the groundwater and an order of magnitude lower in the surface water throughout the year. This study shows very fast immobilisation of dissolved P during the initial stage of the Fe(II) oxidation proces which results in P-depleted water before Fe(II) is competly depleted. This cannot be explained by surface complexation of phosphate to freshly formed Fe-oxyhydroxides but indicates the formation of Fe(III)-phosphate precipitates. The formation of Fe(III)-phosphates at redox gradients seems an important geochemical mechanism in the transformation of dissolved phosphate to particulate phosphate and, therefore, a major control on the P retention in natural waters that drain anaerobic aquifers.

Iron oxidation kinetics and phosphate immobilization along the flow-path from groundwater into surface water

NASA Astrophysics Data System (ADS)

van der Grift, B.; Rozemeijer, J. C.; Griffioen, J.; van der Velde, Y.

2014-11-01

The retention of phosphorus in surface waters through co-precipitation of phosphate with Fe-oxyhydroxides during exfiltration of anaerobic Fe(II) rich groundwater is not well understood. We developed an experimental field set-up to study Fe(II) oxidation and P immobilization along the flow-path from groundwater into surface water in an agricultural experimental catchment of a small lowland river. We physically separated tube drain effluent from groundwater discharge before it entered a ditch in an agricultural field. Through continuous discharge measurements and weekly water quality sampling of groundwater, tube drain water, exfiltrated groundwater, and surface water, we investigated Fe(II) oxidation kinetics and P immobilization processes. The oxidation rate inferred from our field measurements closely agreed with the general rate law for abiotic oxidation of Fe(II) by O2. Seasonal changes in climatic conditions affected the Fe(II) oxidation process. Lower pH and lower temperatures in winter (compared to summer) resulted in low Fe oxidation rates. After exfiltration to the surface water, it took a couple of days to more than a week before complete oxidation of Fe(II) is reached. In summer time, Fe oxidation rates were much higher. The Fe concentrations in the exfiltrated groundwater were low, indicating that dissolved Fe(II) is completely oxidized prior to inflow into a ditch. While the Fe oxidation rates reduce drastically from summer to winter, P concentrations remained high in the groundwater and an order of magnitude lower in the surface water throughout the year. This study shows very fast immobilization of dissolved P during the initial stage of the Fe(II) oxidation process which results in P-depleted water before Fe(II) is completely depleted. This cannot be explained by surface complexation of phosphate to freshly formed Fe-oxyhydroxides but indicates the formation of Fe(III)-phosphate precipitates. The formation of Fe(III)-phosphates at redox gradients seems an important geochemical mechanism in the transformation of dissolved phosphate to structural phosphate and, therefore, a major control on the P retention in natural waters that drain anaerobic aquifers.

A gel probe equilibrium sampler for measuring arsenic porewater profiles and sorption gradients in sediments: II. Field application to Haiwee reservoir sediment

USGS Publications Warehouse

Campbell, K.M.; Root, R.; O'Day, P. A.; Hering, J.G.

2008-01-01

Arsenic (As) geochemistry and sorption behavior were measured in As- and iron (Fe)-rich sediments of Haiwee Reservoir by deploying undoped (clear) polyacrylamide gels and hydrous ferric oxide (HFO)-doped gels in a gel probe equilibrium sampler, which is a novel technique for directly measuring the effects of porewater composition on As adsorption to Fe oxides phases in situ. Arsenic is deposited at the sediment surface as As(V) and is reduced to As(III) in the upper layers of the sediment (0-8 cm), but the reduction of As(V) does not cause mobilization into the porewater. Dissolved As and Fe concentrations increased at depth in the sediment column driven by the reductive dissolution of amorphous Fe(III) oxyhydroxides and conversion to a mixed Fe(II, III) green rust-type phase. Adsorption of As and phosphorous (P) onto HFO-doped gels was inhibited at intermediate depths (10-20 cm), possibly due to dissolved organic or inorganic carbon, indicating that dissolved As concentrations were at least partially controlled by porewater composition rather than surface site availability. In sediments that had been recently exposed to air, the region of sorption inhibition was not observed, suggesting that prior exposure to air affected the extent of reductive dissolution, porewater chemistry, and As adsorption behavior. Arsenic adsorption onto the HFO-doped gels increased at depths >20 cm, and the extent of adsorption was most likely controlled by the competitive effects of dissolved phosphate. Sediment As adsorption capacity appeared to be controlled by changes in porewater composition and competitive effects at shallower depths, and by reductive dissolution and availability of sorption sites at greater burial depths. ?? 2008 American Chemical Society.

Evidence for Microbial Fe(III) Reduction in Anoxic, Mining-Impacted Lake Sediments (Lake Coeur d'Alene, Idaho)

PubMed Central

Cummings, David E.; March, Anthony W.; Bostick, Benjamin; Spring, Stefan; Caccavo, Frank; Fendorf, Scott; Rosenzweig, R. Frank

2000-01-01

Mining-impacted sediments of Lake Coeur d'Alene, Idaho, contain more than 10% metals on a dry weight basis, approximately 80% of which is iron. Since iron (hydr)oxides adsorb toxic, ore-associated elements, such as arsenic, iron (hydr)oxide reduction may in part control the mobility and bioavailability of these elements. Geochemical and microbiological data were collected to examine the ecological role of dissimilatory Fe(III)-reducing bacteria in this habitat. The concentration of mild-acid-extractable Fe(II) increased with sediment depth up to 50 g kg−1, suggesting that iron reduction has occurred recently. The maximum concentrations of dissolved Fe(II) in interstitial water (41 mg liter−1) occurred 10 to 15 cm beneath the sediment-water interface, suggesting that sulfidogenesis may not be the predominant terminal electron-accepting process in this environment and that dissolved Fe(II) arises from biological reductive dissolution of iron (hydr)oxides. The concentration of sedimentary magnetite (Fe3O4), a common product of bacterial Fe(III) hydroxide reduction, was as much as 15.5 g kg−1. Most-probable-number enrichment cultures revealed that the mean density of Fe(III)-reducing bacteria was 8.3 × 105 cells g (dry weight) of sediment−1. Two new strains of dissimilatory Fe(III)-reducing bacteria were isolated from surface sediments. Collectively, the results of this study support the hypothesis that dissimilatory reduction of iron has been and continues to be an important biogeochemical process in the environment examined. PMID:10618217

Diel behavior of iron and other heavy metals in a mountain stream with acidic to neutral pH: Fisher Creek, Montana, USA

USGS Publications Warehouse

Gammons, C.H.; Nimick, D.A.; Parker, S.R.; Cleasby, T.E.; McCleskey, R. Blaine

2005-01-01

Three simultaneous 24-h samplings at three sites over a downstream pH gradient were conducted to examine diel fluctuations in heavy metal concentrations in Fisher Creek, a small mountain stream draining abandoned mine lands in Montana. Average pH values at the upstream (F1), middle (F2), and downstream (F3) monitoring stations were 3.31, 5.46, and 6.80, respectively. The downstream increase in pH resulted in precipitation of hydrous ferric oxide (HFO) and hydrous aluminum oxide (HAO) on the streambed. At F1 and F2, Fe showed strong diel cycles in dissolved concentration and Fe(II)/Fe(III) ratio; these cycles were attributed to daytime photoreduction of Fe(III) to Fe(II), reoxidation of Fe(II) to Fe(III), and temperature-dependent hydrolysis and precipitation of HFO. At the near-neutral downstream station, no evidence of Fe(III) photoreduction was observed, and suspended particles of HFO dominated the total Fe load. HFO precipitation rates between F2 and F3 were highest in the afternoon, due in part to reoxidation of a midday pulse of Fe2+ formed by photoreduction in the upper, acidic portions of the stream. Dissolved concentrations of Fe(II) and Cu decreased tenfold and 2.4-fold, respectively, during the day at F3. These changes were attributed to sorption onto fresh HFO surfaces. Results of surface complexation modeling showed good agreement between observed and predicted Cu concentrations at F3, but only when adsorption enthalpies were added to the thermodynamic database to take into account diel temperature variations. The field and modeling results illustrate that the degree to which trace metals adsorb onto actively forming HFO is strongly temperature dependent. This study is an example of how diel Fe cycles caused by redox and hydrolysis reactions can induce a diel cycle in a trace metal of toxicological importance in downstream waters. Copyright ?? 2005 Elsevier Ltd.

Assessing the concentration, speciation, and toxicity of dissolved metals during mixing of acid-mine drainage and ambient river water downstream of the Elizabeth Copper Mine, Vermont, USA

USGS Publications Warehouse

Balistrieri, L.S.; Seal, R.R.; Piatak, N.M.; Paul, B.

2007-01-01

The authors determine the composition of a river that is impacted by acid-mine drainage, evaluate dominant physical and geochemical processes controlling the composition, and assess dissolved metal speciation and toxicity using a combination of laboratory, field and modeling studies. Values of pH increase from 3.3 to 7.6 and the sum of dissolved base metal (Cd + Co + Cu + Ni + Pb + Zn) concentrations decreases from 6270 to 100 ??g/L in the dynamic mixing and reaction zone that is downstream of the river's confluence with acid-mine drainage. Mixing diagrams and PHREEQC calculations indicate that mixing and dilution affect the concentrations of all dissolved elements in the reach, and are the dominant processes controlling dissolved Ca, K, Li, Mn and SO4 concentrations. Additionally, dissolved Al and Fe concentrations decrease due to mineral precipitation (gibbsite, schwertmannite and ferrihydrite), whereas dissolved concentrations of Cd, Co, Cu, Ni, Pb and Zn decrease due to adsorption onto newly formed Fe precipitates. The uptake of dissolved metals by aquatic organisms is dependent on the aqueous speciation of the metals and kinetics of complexation reactions between metals, ligands and solid surfaces. Dissolved speciation of Cd, Cu, Ni and Zn in the mixing and reaction zone is assessed using the diffusive gradients in thin films (DGT) technique and results of speciation calculations using the Biotic Ligand Model (BLM). Data from open and restricted pore DGT units indicate that almost all dissolved metal species are inorganic and that aqueous labile or DGT available metal concentrations are generally equal to total dissolved concentrations in the mixing zone. Exceptions occur when labile metal concentrations are underestimated due to competition between H+ and metal ions for Chelex-100 binding sites in the DGT units at low pH values. Calculations using the BLM indicate that dissolved Cd and Zn species in the mixing and reaction zone are predominantly inorganic, which is consistent with the DGT results. Although the DGT method indicates that the majority of aqueous Cu species are inorganic, BLM calculations indicate that dissolved Cu is inorganic at pH 5.5. Integrated dissolved labile concentrations of Cd, Cu and Zn in the mixing and reaction zone are compared to calculated acute toxicity concentrations (LC50 values) for fathead minnows (Pimephales promelas) (Cd, Cu and Zn) and water fleas (Ceriodaphnia dubia) (Cd and Cu) using the BLM, and to national recommended water quality criteria [i.e., criteria maximum concentration (CMC) and criterion continuous concentration (CCC)]. Observed labile concentrations of Cd and Zn are below LC50 values and CMC for Cd, but above CCC and CMC for Zn at sites <30 m downstream of the confluence. In contrast, labile Cu concentrations exceed LC50 values for the organisms as well as CCC and CMC at sites <30 m downstream of the confluence. These results suggest that environmental conditions at sites closest to the confluence of the river and acid-mine drainage should not support healthy aquatic organisms. ?? 2007 Elsevier Ltd. All rights reserved.

Preservation of water samples for arsenic(III/V) determinations: An evaluation of the literature and new analytical results

USGS Publications Warehouse

McCleskey, R. Blaine; Nordstrom, D. Kirk; Maest, A.S.

2004-01-01

Published literature on preservation procedures for stabilizing aqueous inorganic As(III/V) redox species contains discrepancies. This study critically evaluates published reports on As redox preservation and explains discrepancies in the literature. Synthetic laboratory preservation experiments and time stability experiments were conducted for natural water samples from several field sites. Any field collection procedure that filters out microorganisms, adds a reagent that prevents dissolved Fe and Mn oxidation and precipitation, and isolates the sample from solar radiation will preserve the As(III/V) ratio. Reagents that prevent Fe and Mn oxidation and precipitation include HCl, H 2SO4, and EDTA, although extremely high concentrations of EDTA are necessary for some water samples high in Fe. Photo-catalyzed Fe(III) reduction causes As(III) oxidation; however, storing the sample in the dark prevents photochemical reactions. Furthermore, the presence of Fe(II) or SO 4 inhibits the oxidation of As(III) by Fe(III) because of complexation reactions and competing reactions with free radicals. Consequently, fast abiotic As(III) oxidation reactions observed in the laboratory are not observed in natural water samples for one or more of the following reasons: (1) the As redox species have already stabilized, (2) most natural waters contain very low dissolved Fe(III) concentrations, (3) the As(III) oxidation caused by Fe(III) photoreduction is inhibited by Fe(II) or SO4.

Groundwater chemistry and occurrence of arsenic in the Meghna floodplain aquifer, southeastern Bangladesh

USGS Publications Warehouse

Zahid, A.; Hassan, M.Q.; Balke, K.-D.; Flegr, M.; Clark, D.W.

2008-01-01

Dissolved major ions and important heavy metals including total arsenic and iron were measured in groundwater from shallow (25-33 m) and deep (191-318 m) tube-wells in southeastern Bangladesh. These analyses are intended to help describe geochemical processes active in the aquifers and the source and release mechanism of arsenic in sediments for the Meghna Floodplain aquifer. The elevated Cl- and higher proportions of Na+ relative to Ca2+, Mg2+, and K+ in groundwater suggest the influence by a source of Na+ and Cl-. Use of chemical fertilizers may cause higher concentrations of NH 4+ and PO 43- in shallow well samples. In general, most ions are positively correlated with Cl-, with Na+ showing an especially strong correlation with Cl-, indicating that these ions are derived from the same source of saline waters. The relationship between Cl-/HCO 3- ratios and Cl- also shows mixing of fresh groundwater and seawater. Concentrations of dissolved HCO 3- reflect the degree of water-rock interaction in groundwater systems and integrated microbial degradation of organic matter. Mn and Fe-oxyhydroxides are prominent in the clayey subsurface sediment and well known to be strong adsorbents of heavy metals including arsenic. All five shallow well samples had high arsenic concentration that exceeded WHO recommended limit for drinking water. Very low concentrations of SO 42- and NO 3- and high concentrations of dissolved Fe and PO 43- and NH 4+ ions support the reducing condition of subsurface aquifer. Arsenic concentrations demonstrate negative co-relation with the concentrations of SO 42- and NO 3- but correlate weakly with Mo, Fe concentrations and positively with those of P, PO 43- and NH 4+ ions. ?? 2007 Springer-Verlag.

The effect of membrane filtration on dissolved trace element concentrations

USGS Publications Warehouse

Horowitz, A.J.; Lum, K.R.; Garbarino, J.R.; Hall, G.E.M.; Lemieux, C.; Demas, C.R.

1996-01-01

The almost universally accepted operational definition for dissolved constituents is based on processing whole-water samples through a 0.45-??m membrane filter. Results from field and laboratory experiments indicate that a number of factors associated with filtration, other than just pore size (e.g., diameter, manufacturer, volume of sample processed, amount of suspended sediment in the sample), can produce substantial variations in the 'dissolved' concentrations of such elements as Fe, Al, Cu, Zn, Pb, Co, and Ni. These variations result from the inclusion/exclusion of colloidally- associated trace elements. Thus, 'dissolved' concentrations quantitated by analyzing filtrates generated by processing whole-water through similar pore- sized membrane filters may not be equal/comparable. As such, simple filtration through a 0.45-??m membrane filter may no longer represent an acceptable operational definition for dissolved chemical constituents. This conclusion may have important implications for environmental studies and regulatory agencies.

Effect of membrane filtration artifacts on dissolved trace element concentrations

USGS Publications Warehouse

Horowitz, Arthur J.; Elrick, Kent A.; Colberg, Mark R.

1992-01-01

Among environment scientists, the current and almost universally accepted definition of dissolved constituents is an operational one; only those materials which pass through a 0.45-??m membrane filter are considered to be dissolved. Detailed laboratory and field studies on Fe and Al indicate that a number of factors associated with filtration, other than just pore size, can substantially alter 'dissolved' trace element concentrations; these include: filter type, filter diameter, filtration method, volume of sample processed, suspended sediment concentration, suspended sediment grain-size distribution, concentration of colloids and colloidally associated trace elements and concentration of organic matter. As such, reported filtered-water concentrations employing the same pore size filter may not be equal. Filtration artifacts may lead to the production of chemical data that indicate seasonal or annual 'dissolved' chemical trends which do not reflect actual environmental conditions. Further, the development of worldwide averages for various dissolved chemical constituents, the quantification of geochemical cycles, and the determination of short- or long-term environmental chemical trends may be subject to substantial errors, due to filtration artifacts, when data from the same or multiple sources are combined. Finally, filtration effects could have a substantial impact on various regulatory requirements.

The effect of membrane filtration artifacts on dissolved trace element concentrations

USGS Publications Warehouse

Horowitz, A.J.; Elrick, K.A.; Colberg, M.R.

1992-01-01

Among environment scientists, the current and almost universally accepted definition of dissolved constituents is an operational one only those materials which pass through a 0.45-??m membrane filter are considered to be dissolved. Detailed laboratory and field studies on Fe and Al indicate that a number of factors associated with filtration, other than just pore size, can substantially alter 'dissolved' trace element concentrations; these include: filter type, filter diameter, filtration method, volume of sample processed, suspended sediment concentration, suspended sediment grain-size distribution, concentration of colloids and colloidally-associated trace elements and concentration of organic matter. As such, reported filtered-water concentrations employing the same pore size filter may not be equal. Filtration artifacts may lead to the production of chemical data that indicate seasonal or annual 'dissolved' chemical trends which do not reflect actual environmental conditions. Further, the development of worldwide averages for various dissolved chemical constituents, the quantification of geochemical cycles, and the determination of short- or long-term environmental chemical trends may be subject to substantial errors, due to filtration artifacts, when data from the same or multiple sources are combined. Finally, filtration effects could have a substantial impact on various regulatory requirements.

Naphthenic acids removal from high TDS produced water by persulfate mediated iron oxide functionalized catalytic membrane, and by nanofiltration.

PubMed

Aher, Ashish; Papp, Joseph; Colburn, Andrew; Wan, Hongyi; Hatakeyama, Evan; Prakash, Prakhar; Weaver, Ben; Bhattacharyya, Dibakar

2017-11-01

Oil industries generate large amounts of produced water containing organic contaminants, such as naphthenic acids (NA) and very high concentrations of inorganic salts. Recovery of potable water from produced water can be highly energy intensive is some cases due to its high salt concentration, and safe discharge is more suitable. Here, we explored catalytic properties of iron oxide (Fe x O y nanoparticles) functionalized membranes in oxidizing NA from water containing high concentrations of total dissolved solids (TDS) using persulfate as an oxidizing agent. Catalytic decomposition of persulfate by Fe x O y functionalized membranes followed pseudo-first order kinetics with an apparent activation energy of 18 Kcal/mol. Fe x O y functionalized membranes were capable of lowering the NA concentrations to less than discharge limits of 10 ppm at 40 °C. Oxidation state of iron during reaction was quantified. Membrane performance was investigated for extended period of time. A coupled process of advanced oxidation catalyzed by membrane and nanofiltration was also evaluated. Commercially available nanofiltration membranes were found capable of retaining NA from water containing high concentrations of dissolved salts. Commercial NF membranes, Dow NF270 (Dow), and NF8 (Nanostone) had NA rejection of 79% and 82%, respectively. Retentate for the nanofiltration was further treated with advanced oxidation catalyzed by Fe x O y functionalized membrane for removal of NA.

Oxic limestone drains for treatment of dilute, acidic mine drainage

USGS Publications Warehouse

Cravotta, Charles A.

1998-01-01

Limestone treatment systems can be effective for remediation of acidic mine drainage (AMD) that contains moderate concentrations of dissolved O2 , Fe3+ , or A13+ (1‐5 mg‐L‐1 ). Samples of water and limestone were collected periodically for 1 year at inflow, outflow, and intermediate points within underground, oxic limestone drains (OLDs) in Pennsylvania to evaluate the transport of dissolved metals and the effect of pH and Fe‐ and Al‐hydrolysis products on the rate of limestone dissolution. The influent was acidic and relatively dilute (pH <4; acidity < 90 mg‐L‐1 ) but contained 1‐4 mg‐L‐1 Of O2 , Fe3+ , A13+ , and Mn2+ . The total retention time in the OLDs ranged from 1.0 to 3.1 hours. Effluent remained oxic (02 >1 mg‐L‐1 ) but was near neutral (pH = 6.2‐7.0); Fe and Al decreased to less than 5% of influent concentrations. As pH increased near the inflow, hydrous Fe and Al oxides precipitated in the OLDs. The hydrous oxides, nominally Fe(OH)3 and AI(OH)3, were visible as loosely bound, orange‐yellow coatings on limestone near the inflow. As time elapsed, Fe(OH)3 and AI(OH)3 particles were transported downflow. During the first 6 months of the experiment, Mn 2+ was transported conservatively through the OLDs; however, during the second 6 months, concentrations of Mn in effluent decreased by about 50% relative to influent. The accumulation of hydrous oxides and elevated pH (>5) in the downflow part of the OLDs promoted sorption and coprecipitation of Mn as indicated by its enrichment relative to Fe in hydrous‐oxide particles and coatings on limestone. Despite thick (~1 mm) hydrous‐oxide coatings on limestone near the inflow, CaCO3 dissolution was more rapid near the inflow than at downflow points within the OLD where the limestone was not coated. The rate of limestone dissolution decreased with increased residence time, pH, and concentrations of Ca2+ and HCO3‐ and decreased PCO2. The following overall reaction shows alkalinity as an ultimate product of the iron hydrolysis reaction in an OLD:Fe2+ + 0.25 O2 +CaCO3 + 2.5 H2O --> Fe(OH)3 + 2 Ca2+ + 2 HCO3-where 2 moles of CaCO3 dissolve for each mole of Fe(OH)3 produced. Hence, in an OLD, rapidly dissolving limestone surfaces are not stable substrates for Fe(OH)3 attachment and armoring. Because overall efficiency is increased by combining neutralization and hydrolysis reactions, an OLD followed by a settling pond requires less land area than needed for a two‐stage treatment system consisting of an anoxic limestone drain an oxidation‐settling pond or wetland. To facilitate removal of hydrous‐oxide sludge, a perforated‐pipe subdrain can be installed within an OLD.

Investigation of iron(III) reduction and trace metal interferences in the determination of dissolved iron in seawater using flow injection with luminol chemiluminescence detection.

PubMed

Ussher, Simon J; Milne, Angela; Landing, William M; Attiq-ur-Rehman, Kakar; Séguret, Marie J M; Holland, Toby; Achterberg, Eric P; Nabi, Abdul; Worsfold, Paul J

2009-10-12

A detailed investigation into the performance of two flow injection-chemiluminescence (FI-CL) manifolds (with and without a preconcentration column) for the determination of sub-nanomolar dissolved iron (Fe(II)+Fe(III)), following the reduction of Fe(III) by sulphite, in seawater is described. Kinetic experiments were conducted to examine the efficiency of reduction of inorganic Fe(III) with sulphite under different conditions and a rigorous study of the potential interference caused by other transition metals present in seawater was conducted. Using 100microM concentrations of sulphite a reduction time of 4h was sufficient to quantitatively reduce Fe(III) in seawater. Under optimal conditions, cobalt(II) and vanadium(IV)/(III) were the major positive interferences and strategies for their removal are reported. Specifically, cobalt(II) was masked by the addition of dimethylglyoxime to the luminol solution and vanadium(IV) was removed by passing the sample through an 8-hydroxyquinoline column in a low pH carrier stream. Manganese(II) also interfered by suppression of the CL response but this was not significant at typical open ocean concentrations.

No effect of H2O degassing on the oxidation state of hydrous rhyolite magmas: a comparison of pre- and post-eruptive Fe2+ concentrations in six obsidian samples from the Mexican and Cascade arcs

NASA Astrophysics Data System (ADS)

Waters, L.; Lange, R. A.

2011-12-01

The extent to which degassing affects the oxidation state of arc magmas is widely debated. Several researchers have examined how degassing of mixed H-C-O-S-Cl fluids may change the Fe3+/FeT ratio of magmas, and it has been proposed that degassing may induce either oxidation or reduction depending on the initial oxidation state. A commonly proposed oxidation reaction is related to H2O degassing: H2O (melt) + 2FeO (melt) = H2 (fluid) + Fe2O3 (melt). Another mechanism by which H2O degassing can affect the iron redox state is if dissolved water affects the activity of ferrous and/or ferric iron in the melt. Although Moore et al. (1995) presented experiments showing no evidence of an affect of dissolved water on the activity of the ferric-ferrous ratio in silicate melts, other experimental results (e.g., Baker and Rutherford, 1996; Gaillard et al., 2001; 2003) indicate that there may be such an effect in rhyolite liquids. It has long been understood that rhyolites, owing to their low total iron concentrations, are more sensitive than other magma types to degassing-induced change in redox state. Therefore, a rigorous test of whether H2O degassing affects the redox state of arc magmas is best evaluated on rhyolites. In this study, a comparison is made between the pre-eruptive (pre-degassing) Fe2+ concentrations in six, phenocryst-poor (<5%), fresh, glassy obsidian samples with their post-eruptive (post-degassing) Fe2+ concentrations. Near-liquidus co-precipitation of two Fe-Ti oxides allows the pre-eruptive oxygen fugacity and temperature to be calculated in each rhyolite using the oxygen barometer and thermometer of Ghiorso and Evans (2008). Temperatures range from 793 (± 19) to 939 (± 15) °C, and ΔNNO values (log10fO2 of sample - log10fO2 of Ni-NiO buffer) range from -0.4 to +1.4. These ΔNNO values allow the ferric-ferrous ratio in the liquid to be calculated, using the experimental calibration of Kress and Carmichael (1991), which relates melt composition (not including dissolved water), oxygen fugacity and temperature to melt ferric-ferrous ratios. With temperature known, the plagioclase-liquid hygrometer of Lange et al. (2009) was applied and maximum melt water concentrations range from 4.2 to 7.5 wt%. Both the oxidation state and water concentration are known prior to eruption, at the time of phenocryst growth. After eruption, the rhyolites lost nearly all of their volatiles, as indicated by the low loss on ignition values (LOI ≤ 0.7 wt%). In order to test how much oxidation of ferrous iron occurred as a consequence of that degassing, we measured the ferrous iron concentration in the bulk samples by titration, using the Wilson (1960) method, which was successfully tested again three USGS and one Canadian Geological Survey standards. Our results indicate no detectable change within analytical error between pre- and post-eruptive FeO concentrations, with an average deviation of 0.09 wt% and a maximum deviation of 0.15 wt%. Our results show that H2O degassing has no effect on the redox state of rhyolite magmas, which requires that dissolved water has no resolvable affect on the activity ratio of the iron oxide components in melt.

In situ analysis of oxygen consumption and diffusive transport in high-temperature acidic iron-oxide microbial mats.

PubMed

Bernstein, Hans C; Beam, Jacob P; Kozubal, Mark A; Carlson, Ross P; Inskeep, William P

2013-08-01

The role of dissolved oxygen as a principal electron acceptor for microbial metabolism was investigated within Fe(III)-oxide microbial mats that form in acidic geothermal springs of Yellowstone National Park (USA). Specific goals of the study were to measure and model dissolved oxygen profiles within high-temperature (65-75°C) acidic (pH = 2.7-3.8) Fe(III)-oxide microbial mats, and correlate the abundance of aerobic, iron-oxidizing Metallosphaera yellowstonensis organisms and mRNA gene expression levels to Fe(II)-oxidizing habitats shown to consume oxygen. In situ oxygen microprofiles were obtained perpendicular to the direction of convective flow across the aqueous phase/Fe(III)-oxide microbial mat interface using oxygen microsensors. Dissolved oxygen concentrations dropped from ∼ 50-60 μM in the bulk-fluid/mat surface to below detection (< 0.3 μM) at a depth of ∼ 700 μm (∼ 10% of the total mat depth). Net areal oxygen fluxes into the microbial mats were estimated to range from 1.4-1.6 × 10(-4)  μmol cm(-2)  s(-1) . Dimensionless parameters were used to model dissolved oxygen profiles and establish that mass transfer rates limit the oxygen consumption. A zone of higher dissolved oxygen at the mat surface promotes Fe(III)-oxide biomineralization, which was supported using molecular analysis of Metallosphaera yellowstonensis 16S rRNA gene copy numbers and mRNA expression of haem Cu oxidases (FoxA) associated with Fe(II)-oxidation. © 2013 John Wiley & Sons Ltd and Society for Applied Microbiology.

Inhibition of bacterial oxidation of ferrous iron by lead nitrate in sulfate-rich systems.

PubMed

Wang, Hongmei; Gong, Linfeng; Cravotta, Charles A; Yang, Xiaofen; Tuovinen, Olli H; Dong, Hailiang; Fu, Xiang

2013-01-15

Inhibition of bacterial oxidation of ferrous iron (Fe(II)) by Pb(NO(3))(2) was investigated with a mixed culture of Acidithiobacillus ferrooxidans. The culture was incubated at 30 °C in ferrous-sulfate medium amended with 0-24.2 mM Pb(II) added as Pb(NO(3))(2). Anglesite (PbSO(4)) precipitated immediately upon Pb addition and was the only solid phase detected in the abiotic controls. Both anglesite and jarosite (KFe(3)(SO(4))(2)(OH)(6)) were detected in inoculated cultures. Precipitation of anglesite maintained dissolved Pb concentrations at 16.9-17.6 μM regardless of the concentrations of Pb(NO(3))(2) added. Fe(II) oxidation was suppressed by 24.2 mM Pb(NO(3))(2) addition even when anglesite was removed before inoculation. Experiments with 0-48 mM KNO(3) demonstrated that bacterial Fe(II) oxidation decreased as nitrate concentration increased. Therefore, inhibition of Fe(II) oxidation at 24.2 mM Pb(NO(3))(2) addition resulted from nitrate toxicity instead of Pb addition. Geochemical modeling that considered the initial precipitation of anglesite to equilibrium followed by progressive oxidation of Fe(II) and the precipitation of jarosite and an amorphous iron hydroxide phase, without allowing plumbojarosite to precipitate were consistent with the experimental time-series data on Fe(II) oxidation under biotic conditions. Anglesite precipitation in mine tailings and other sulfate-rich systems maintains dissolved Pb concentrations below the toxicity threshold of A. ferrooxidans. Copyright © 2012 Elsevier B.V. All rights reserved.

Groundwater arsenic and fluoride in Rajnandgaon District, Chhattisgarh, northeastern India

NASA Astrophysics Data System (ADS)

Patel, Khageshwar Singh; Sahu, Bharat Lal; Dahariya, Nohar Singh; Bhatia, Amarpreet; Patel, Raj Kishore; Matini, Laurent; Sracek, Ondra; Bhattacharya, Prosun

2017-07-01

The groundwater of Ambagarh Chouki, Rajnandgaon, India, shows elevated levels of As and F-, frequently above the WHO guidelines. In this work, the concentrations of As, F-, Na+, Mg2+, Ca2+, Cl-, SO4 2-, HCO3 -, Fe, dissolved organic carbon (DOC) and dissolved inorganic carbon (DIC) in the groundwater of Ambagarh Chouki are described. The sources of dissolved components in the groundwater are investigated using the cluster and factor analysis. Five factors have been identified and linked to processes responsible for the formation of groundwater chemistry. High concentrations of dissolved As seems to be linked to high concentrations of DOC, suggesting reductive dissolution of ferric oxyhydroxides as arsenic mobilization process. Fluoride is found in shallow depth water, presumably as a consequence of evaporation of water and removal of Ca2+ by precipitation of carbonates.

Seasonal changes in Fe along a glaciated Greenlandic fjord.

NASA Astrophysics Data System (ADS)

Hopwood, Mark; Connelly, Douglas; Arendt, Kristine; Juul-Pedersen, Thomas; Stinchcombe, Mark; Meire, Lorenz; Esposito, Mario; Krishna, Ram

2016-03-01

Greenland's ice sheet is the second largest on Earth, and is under threat from a warming Arctic climate. An increase in freshwater discharge from Greenland has the potential to strongly influence the composition of adjacent water masses with the largest impact on marine ecosystems likely to be found within the glaciated fjords. Here we demonstrate that physical and chemical estuarine processes within a large Greenlandic fjord are critical factors in determining the fate of meltwater derived nutrients and particles, especially for non-conservative elements such as Fe. Concentrations of Fe and macronutrients in surface waters along Godthåbsfjord, a southwest Greenlandic fjord with freshwater input from 6 glaciers, changed markedly between the onset and peak of the meltwater season due to the development of a thin (<10 m), outflowing, low-salinity surface layer. Dissolved (<0.2 µm) Fe concentrations in meltwater entering Godthåbsfjord (200 nM), in freshly melted glacial ice (mean 38 nM) and in surface waters close to a land terminating glacial system (80 nM) all indicated high Fe inputs into the fjord in summer. Total dissolvable (unfiltered at pH <2.0) Fe was similarly high with concentrations always in excess of 100 nM throughout the fjord and reaching up to 5.0 µM close to glacial outflows in summer. Yet, despite the large seasonal freshwater influx into the fjord, Fe concentrations near the fjord mouth in the out-flowing surface layer were similar in summer to those measured before the meltwater season. Furthermore, turbidity profiles indicated that sub-glacial particulate Fe inputs may not actually mix into the outflowing surface layer of this fjord. Emphasis has previously been placed on the possibility of increased Fe export from Greenland as meltwater fluxes increase. Here we suggest that in-fjord processes may be effective at removing Fe from surface waters before it can be exported to coastal seas.

Comparison of Eh and H2 measurements for delineating redox processes in a contaminated aquifer

USGS Publications Warehouse

Chapelle, Francis H.; Haack, Sheridan K.; Adriaens, Peter; Henry, Mark A.; Bradley, Paul M.

1996-01-01

Measurements of oxidation-reduction potential (Eh) and concentrations of dissolved hydrogen (H2) were made in a shallow groundwater system contaminated with solvents and jet fuel to delineate the zonation of redox processes. Eh measurements ranged from +69 to -158 mV in a cross section of the contaminated plume and accurately delineated oxic from anoxic groundwater. Plotting measured Eh and pH values on an equilibrium stability diagram indicated that Fe(III) reduction was the predominant redox process in the anoxic zone and did not indicate the presence of methanogenesis and sulfate reduction. In contrast, measurements of H2concentrations indicated that methanogenesis predominated in heavily contaminated sediments near the water table surface (H2 ∼ 7.0 nM) and that the methanogenic zone was surrounded by distinct sulfate-reducing (H2 ∼ 1-4 nM) and Fe(III)-reducing (H2 ∼ 0.1-0.8 nM) zones. The presence of methanogenesis, sulfate reduction, and Fe(III) reduction was confirmed by the distribution of dissolved oxygen, sulfate, Fe(II), and methane in groundwater. These results show that H2 concentrations were more useful for identifying anoxic redox processes than Ehmeasurements in this groundwater system. However, H2-based redox zone delineations are more reliable when H2 concentrations are interpreted in the context of electron-acceptor (oxygen, nitrate, sulfate) availability and the presence of final products [Fe(II), sulfide, methane] of microbial metabolism.

Effect of iron on inhibition of acid demineralisation of bovine dental enamel in vitro.

PubMed

Buzalaf, Marília Afonso Rabelo; de Moraes Italiani, Flávia; Kato, Melissa Thiemi; Martinhon, Cleide Cristina Rodrigues; Magalhães, Ana Carolina

2006-10-01

Iron ions (Fe(2+)) have been shown to be cariostatic in many studies particularly by their ability to reduce bacterial metabolism. Nevertheless, the role of iron ions on dissolution of enamel is unexplored. The aim of the present study was therefore to investigate the protective effect of increasing concentrations (0-120mmol/L) of Fe(2+) on the dissolution of enamel. Enamel powder was subjected to acetic acid made with increasing concentrations with respect to FeSO(4)x7H(2)O. In order to determine the amount of enamel dissolved, the phosphate released in the medium was analysed spectrophotometrically using the Fiske-Subarrow method. Data were tested using Kruskall-Wall and Dunn's tests (p<0.05). The degree of protection was found to approach maximum at about 15mmol/L Fe(2+). Higher concentrations of Fe(2+) did not have an extra effect on inhibition of dissolution of enamel powder. In the next step, the protective effect of 15mmol/L Fe(2+) against mineral dissolution of the bovine enamel was evaluated using a simple abiotic model system. Enamel blocks were exposed to a sequence of seven plastic vials, each containing 1mL of 10mmol/L acetic acid. The acid in vial 4 was made 15mmol/L with respect to FeSO(4)x7H(2)O. The mineral dissolved during each challenge was thus determined by phosphate released as described above. Data were tested using two-way ANOVA (p<0.05). Lower demineralisation (around 45%) was found in vial 4 (with Fe) that continued stable until vial 7. Thus, our data suggest that Fe(2+) can be effective on inhibition of dissolution of enamel and that this effect may be durable.

Influence of humic acid on the removal of arsenate and arsenic by ferric chloride: effects of pH, As/Fe ratio, initial As concentration, and co-existing solutes.

PubMed

Kong, Yanli; Kang, Jing; Shen, Jimin; Chen, Zhonglin; Fan, Leitao

2017-01-01

The influence of humic acid (HA) on the removal of arsenic by FeCl 3 was systematically studied in this paper. Jar tests were performed to investigate the influence on arsenic during FeCl 3 coagulation of the pH adjusting method, the initial As/Fe ratio, the equilibrium As concentration, and co-occurring anions and cations. Compared with results in HA-free systems, the removal trends of arsenic in HA solutions were quite different. It was found that As(V) removal was higher at low equilibrium concentration, yet the opposite was true for As(III) removal. The presence of HA influenced the effective number of active sites for arsenic removal by FeCl 3 flocculation. In addition, in the presence of HA, the impacts of co-existing solutions on arsenic removal were also different from that of an HA-free system. This study examined the influence of co-occurring anions, such as phosphate, sulfate, and silicate on arsenic removal, depending on their ability to compete for sorption sites and to hinder or facilitate the aggregation of ferric hydroxide flocs. The presence of Ca 2+ or Cd 2+ significantly increased arsenic removal at higher pH. Low concentrations of dissolved HA and high concentrations of colloid affected the adsorption of arsenic onto iron oxide. The influence of HA on the adsorption of arsenic onto iron oxide primarily depended on the relative content of the dissolved and mineral combination states of HA and the interface combination forms.

Removal of elevated level of chromium in groundwater by the fabricated PANI/Fe3O4 nanocomposites.

PubMed

Ramachandran, Aruna; Prasankumar, T; Sivaprakash, S; Wiston, Biny R; Biradar, Santhosh; Jose, Sujin

2017-03-01

In this work, we report the reduction of chromium concentration in the polluted groundwater samples from Madurai Kamaraj University area, India, where the dissolved salts in groundwater are reported as serious health hazards for its inhabitants. The water samples have intolerable amounts of total dissolved solids (TDS) and chromium is a prominent pollutant among them. Chromium reduction was achieved by treating the polluted groundwater with PANI/Fe 3 O 4 nanocomposites synthesized by in situ polymerization method. Further experimentation showed that the nanocomposites exhibit better chromium removal characteristics upon increasing the aniline concentration during the synthesis. We were able to reduce chromium concentration in the samples from 0.295 mg L -1 to a tolerable amount of 0.144 mg L -1 . This work is expected to open doors for chromium-free groundwater in various regions of India, when improved to an industrial scale.

The cycling of iron, zinc and cadmium in the North East Pacific Ocean - Insights from stable isotopes

NASA Astrophysics Data System (ADS)

Conway, Tim M.; John, Seth G.

2015-09-01

Dissolved stable isotope ratios of the transition metals provide useful information, both for understanding the cycling of these bioactive trace elements through the oceans, and tracing their marine sources and sinks. Here, we present seawater dissolved Fe, Zn and Cd concentration and stable isotope ratio (δ56Fe, δ66Zn, and δ114Cd) profiles from two stations in the Pacific Ocean, the SAFe Station (30°N 140°W) in the subtropical North East Pacific from the GEOTRACES IC2 cruise, and the marginal San Pedro Basin (33.8°N 118.4°W) within the South California Bight. These data represent, to our knowledge, the first full-water column profiles for δ66Zn and δ56Fe from the open-ocean North Pacific, and the first observations of dissolved δ66Zn and δ114Cd in a low-oxygen marginal basin. At the SAFe station, δ56Fe is isotopically lighter throughout the water column (-0.6 to +0.1‰, relative to IRRM-014) compared to the North Atlantic, suggesting significant differences in Fe sources or Fe cycling between these two ocean basins. A broad minimum in δ56Fe associated with the North Pacific oxygen minimum zone (OMZ; <75 μmol kg-1 dissolved oxygen; ∼550-2000 m depth) is consistent with reductive sediments along the California margin being an important source of dissolved Fe to the North Pacific. Other processes which may influence δ56Fe at SAFe include biological cycling in the upper ocean, and input of Fe from hydrothermal vents and oxic sediments below the OMZ. Zn and Cd concentration profiles at both stations broadly match the distribution of the macronutrients silicate and phosphate, respectively. At SAFe, δ114Cd increases towards the surface, reflecting the biological preference for assimilation of lighter Cd isotopes, while negative Cd∗ (-0.12) associated with low oxygen waters supports the recently proposed hypothesis of water-column CdS precipitation. In contrast to δ114Cd, δ66Zn at SAFe decreases towards the surface ocean, perhaps due to scavenging of isotopically heavy Zn, while at intermediate depths δ66Zn provides further evidence of a mid-depth dissolved δ66Zn maximum. We suggest this may be a global feature of Zn biogeochemistry related to either regeneration of heavy adsorbed Zn, or to ZnS formation and removal within the water column. Data from San Pedro shows that anoxic sediments can be a source of isotopically light Zn to the water column (δ66Zn of ∼-0.3‰ relative to JMC Lyon), though evidence of this signal is not observed being transported to SAFe. Within North Pacific Intermediate Water at SAFe (NPIW; ∼500 m) elevated Cd∗ and Zn∗ and a focused minimum in δ56Fe suggest possible transport of Fe, Zn, and Cd over thousands of km from subpolar waters, meaning that NPIW may have a strong influence on the subsurface distribution of trace metals throughout the North Pacific.

Observed and modeled seasonal trends in dissolved and particulate Cu, Fe, Mn, and Zn in a mining-impacted stream.

PubMed

Butler, Barbara A; Ranville, James F; Ross, Philippe E

2008-06-01

North Fork Clear Creek (NFCC) in Colorado, an acid-mine drainage (AMD) impacted stream, was chosen to examine the distribution of dissolved and particulate Cu, Fe, Mn, and Zn in the water column, with respect to seasonal hydrologic controls. NFCC is a high-gradient stream with discharge directly related to snowmelt and strong seasonal storms. Additionally, conditions in the stream cause rapid precipitation of large amounts of hydrous iron oxides (HFO) that sequester metals. Because AMD-impacted systems are complex, geochemical modeling may assist with predictions and/or confirmations of processes occurring in these environments. This research used Visual-MINTEQ to determine if field data collected over a two and one-half year study would be well represented by modeling with a currently existing model, while limiting the number of processes modeled and without modifications to the existing model's parameters. Observed distributions between dissolved and particulate phases in the water column varied greatly among the metals, with average dissolved fractions being >90% for Mn, approximately 75% for Zn, approximately 30% for Cu, and <10% for Fe. A strong seasonal trend was observed for the metals predominantly in the dissolved phase (Mn and Zn), with increasing concentrations during base-flow conditions and decreasing concentrations during spring-runoff. This trend was less obvious for Cu and Fe. Within hydrologic seasons, storm events significantly influenced in-stream metals concentrations. The most simplified modeling, using solely sorption to HFO, gave predicted percentage particulate Cu results for most samples to within a factor of two of the measured values, but modeling data were biased toward over-prediction. About one-half of the percentage particulate Zn data comparisons fell within a factor of two, with the remaining data being under-predicted. Slightly more complex modeling, which included dissolved organic carbon (DOC) as a solution phase ligand, significantly reduced the positive bias between observed and predicted percentage particulate Cu, while inclusion of hydrous manganese oxide (HMO) yielded model results more representative of the observed percentage particulate Zn. These results indicate that there is validity in the use of an existing model, without alteration and with typically collected water chemistry data, to describe complex natural systems, but that processes considered optimal for one metal might not be applicable for all metals in a given water sample.

Meta-omic signatures of microbial metal and nitrogen cycling in marine oxygen minimum zones

PubMed Central

Glass, Jennifer B.; Kretz, Cecilia B.; Ganesh, Sangita; Ranjan, Piyush; Seston, Sherry L.; Buck, Kristen N.; Landing, William M.; Morton, Peter L.; Moffett, James W.; Giovannoni, Stephen J.; Vergin, Kevin L.; Stewart, Frank J.

2015-01-01

Iron (Fe) and copper (Cu) are essential cofactors for microbial metalloenzymes, but little is known about the metalloenyzme inventory of anaerobic marine microbial communities despite their importance to the nitrogen cycle. We compared dissolved O2, NO3−, NO2−, Fe and Cu concentrations with nucleic acid sequences encoding Fe and Cu-binding proteins in 21 metagenomes and 9 metatranscriptomes from Eastern Tropical North and South Pacific oxygen minimum zones and 7 metagenomes from the Bermuda Atlantic Time-series Station. Dissolved Fe concentrations increased sharply at upper oxic-anoxic transition zones, with the highest Fe:Cu molar ratio (1.8) occurring at the anoxic core of the Eastern Tropical North Pacific oxygen minimum zone and matching the predicted maximum ratio based on data from diverse ocean sites. The relative abundance of genes encoding Fe-binding proteins was negatively correlated with O2, driven by significant increases in genes encoding Fe-proteins involved in dissimilatory nitrogen metabolisms under anoxia. Transcripts encoding cytochrome c oxidase, the Fe- and Cu-containing terminal reductase in aerobic respiration, were positively correlated with O2 content. A comparison of the taxonomy of genes encoding Fe- and Cu-binding vs. bulk proteins in OMZs revealed that Planctomycetes represented a higher percentage of Fe genes while Thaumarchaeota represented a higher percentage of Cu genes, particularly at oxyclines. These results are broadly consistent with higher relative abundance of genes encoding Fe-proteins in the genome of a marine planctomycete vs. higher relative abundance of genes encoding Cu-proteins in the genome of a marine thaumarchaeote. These findings highlight the importance of metalloenzymes for microbial processes in oxygen minimum zones and suggest preferential Cu use in oxic habitats with Cu > Fe vs. preferential Fe use in anoxic niches with Fe > Cu. PMID:26441925

Meta-omic signatures of microbial metal and nitrogen cycling in marine oxygen minimum zones.

PubMed

Glass, Jennifer B; Kretz, Cecilia B; Ganesh, Sangita; Ranjan, Piyush; Seston, Sherry L; Buck, Kristen N; Landing, William M; Morton, Peter L; Moffett, James W; Giovannoni, Stephen J; Vergin, Kevin L; Stewart, Frank J

2015-01-01

Iron (Fe) and copper (Cu) are essential cofactors for microbial metalloenzymes, but little is known about the metalloenyzme inventory of anaerobic marine microbial communities despite their importance to the nitrogen cycle. We compared dissolved O2, NO[Formula: see text], NO[Formula: see text], Fe and Cu concentrations with nucleic acid sequences encoding Fe and Cu-binding proteins in 21 metagenomes and 9 metatranscriptomes from Eastern Tropical North and South Pacific oxygen minimum zones and 7 metagenomes from the Bermuda Atlantic Time-series Station. Dissolved Fe concentrations increased sharply at upper oxic-anoxic transition zones, with the highest Fe:Cu molar ratio (1.8) occurring at the anoxic core of the Eastern Tropical North Pacific oxygen minimum zone and matching the predicted maximum ratio based on data from diverse ocean sites. The relative abundance of genes encoding Fe-binding proteins was negatively correlated with O2, driven by significant increases in genes encoding Fe-proteins involved in dissimilatory nitrogen metabolisms under anoxia. Transcripts encoding cytochrome c oxidase, the Fe- and Cu-containing terminal reductase in aerobic respiration, were positively correlated with O2 content. A comparison of the taxonomy of genes encoding Fe- and Cu-binding vs. bulk proteins in OMZs revealed that Planctomycetes represented a higher percentage of Fe genes while Thaumarchaeota represented a higher percentage of Cu genes, particularly at oxyclines. These results are broadly consistent with higher relative abundance of genes encoding Fe-proteins in the genome of a marine planctomycete vs. higher relative abundance of genes encoding Cu-proteins in the genome of a marine thaumarchaeote. These findings highlight the importance of metalloenzymes for microbial processes in oxygen minimum zones and suggest preferential Cu use in oxic habitats with Cu > Fe vs. preferential Fe use in anoxic niches with Fe > Cu.

Iron Cycling in Sediment of the North Atlantic: Preliminary Results from R/V Knorr Expedition 223

NASA Astrophysics Data System (ADS)

Anderson, C. H.; Estes, E. R.; Dyar, M. D.; Murray, R. W.; Spivack, A. J.; Sauvage, J.; McKinley, C. C.; Present, T. M.; Homola, K.; Pockalny, R. A.; D'Hondt, S.

2015-12-01

Iron (Fe) in marine sediments is a significant microbial electron acceptor [Fe(III)] in suboxic conditions and is an electron donor [Fe(II)] in oxic conditions. In the transition from oxic to suboxic sediment, a portion of solid Fe is reduced and mobilized as soluble Fe(II) into interstitial water during the oxidation of organic matter. The presence of Fe and its oxidation state in oxic sediment provides insight into an important metabolic and mineral reaction pathway in subseafloor sediment. We recovered bulk sediment and interstitial water at western North Atlantic sites during Expedition 223 on the R/V Knorr in November, 2014. The expedition targeted regions with predominantly oxic sediment and regions with predominantly anoxic sediment, ideal for investigating redox Fe cycling between solid and aqueous phases. At Site 10 (14.4008N, 50.6209W, 4455m water depth), interstitial dissolved oxygen is depleted within the upper few meters of sediment. At Site 12 (29.6767N, 58.3285W, 5637m water depth), interstitial dissolved oxygen is present throughout the cored sediment column (10s of meters). Here we present total solid Fe concentration for 45 bulk sediment samples and total aqueous Fe and Mn concentrations for 50 interstitial water samples analyzed via ICP-ES. We additionally present Fe(II) and Fe(III) speciation results from 10 solid sediment samples determined by Mossbauer spectroscopy. We trace downcore fluctuations in Fe in solid and aqueous phases to understand Fe cycling in oxic, suboxic, and transitional regimes. Our preliminary data indicate that solid Fe concentration ranges from 4-6 wt % at the oxic site; aqueous Fe ranges from below detection to 20μM and aqueous Mn ranges from 1 to 125 μM at the anoxic site. In the anoxic sediment (Site 10), 86-90% of the total Fe is oxidized [Fe(III)] and 10-14% as reduced [Fe(II)], compared to 3-6% as reduced [Fe(II)] at the oxic site (Site 12), even in sediment as old as 25 million years.

An integrated approach to asses origin and mobilization of As, Fe and Mn in groundwater: the case study of Cremona (northern Italy)

NASA Astrophysics Data System (ADS)

Rotiroti, Marco; Bonomi, Tullia; Fumagalli, Letizia

2013-04-01

The present work concerns the analysis of the hydrogeology and the hydrogeochemistry of the As, Fe, Mn rich groundwater of the alluvial multi-layer aquifer in the lower Po Plain of Cremona (northern Italy). In this analysis, an integrated approach is applied in order to understand the origins (natural or anthropic) and chemical mechanisms of high groundwater As, Fe and Mn concentrations found in the study area. The study area covers a 50 km2 wide area around the urban territory of Cremona. It is located near the confluence between Adda and Po rivers. The multi-aquifer system which interests the first 200-250 m of depth is investigated. The integrated approach involves the (a) collection of historical data related to water quality, water levels and well logs; (b) storage of collected data in specific databases and geographical information systems; (c) design and execution of two field surveys of water levels and water quality, realized in July 2010 and July 2012, concerning also groundwater sampling for isotope and microbiological analysis; (d) construction of a 3D model of aquifer hydrogeological properties (deposits texture, hydraulic conductivity and effective porosity), built by means of ordinary kriging interpolation of numerical values derived from the coding of well logs; (e) analysis of the hydrodynamic properties of the system on the basis of the field measurements; (f) analysis of water quality data (both field and historical data) considering the hydrogeological and hydrodynamic properties of the aquifer system; (g) analysis of isotope and microbiological measurements; (h) implementation of a 1D reactive transport model in order to better understand the hydrogeochemical mechanisms in the system; (i) elaboration of a general hydrogeochemical conceptual model concerning possible origins and chemical mechanisms for the high groundwater As, Fe, Mn and NH4 concentrations, considering also possible anthropogenic influences; (j) development of management tools, as natural background levels (NBL) derivation, supporting groundwater resources protection by public authorities. This approach allows to assume the process of natural organic matter degradation (i.e. peat) as primary control factor on high As, Fe, Mn and NH4 concentrations. Degradation of peat is associated with the consecutive reduction of O2, NO3-, Mn(IV), Fe(III), SO42-, CO2. The reductive dissolution of Mn and Fe oxides (contained in the aquifer sediments) leads to high concentrations of dissolved Fe and Mn, but also to high concentrations of dissolved As, which is generally sorbed on Mn and Fe oxides. Dissolved As concentration can be also lowered by different processes (co-precipitation of As in iron sulfides, precipitation of arsenic sulfides, sorption of As on the remaining Fe-oxides and Mn-oxides, etc.). NH4 is released from the degradation of organic nitrogen of peat. Therefore, a natural origin of As, Fe, Mn and NH4 can be assumed. In addiction, anthropogenic influences on groundwater As, Fe, Mn and NH4 concentrations are locally identified in two sites located in the study area, that are affected by hydrocarbons and organic leachate pollution.

Transport and cycling of iron and hydrogen peroxide in a freshwater stream: Influence of organic acids

USGS Publications Warehouse

Scott, Durelle T.; Runkel, Robert L.; McKnight, Diane M.; Voelker, Bettina M.; Kimball, Briant A.; Carraway, Elizabeth R.

2003-01-01

An in-stream injection of two dissolved organic acids (phthalic and aspartic acids) was performed in an acidic mountain stream to assess the effects of organic acids on Fe photoreduction and H2O2 cycling. Results indicate that the fate of Fe is dependent on a net balance of oxidative and reductive processes, which can vary over a distance of several meters due to changes in incident light and other factors. Solution phase photoreduction rates were high in sunlit reaches and were enhanced by the organic acid addition but were also limited by the amount of ferric iron present in the water column. Fe oxide photoreduction from the streambed and colloids within the water column resulted in an increase in the diurnal load of total filterable Fe within the experimental reach, which also responded to increases in light and organic acids. Our results also suggest that Fe(II) oxidation increased in response to the organic acids, with the result of offsetting the increase in Fe(II) from photoreductive processes. Fe(II) was rapidly oxidized to Fe(III) after sunset and during the day within a well-shaded reach, presumably through microbial oxidation. H2O 2, a product of dissolved organic matter photolysis, increased downstream to maximum concentrations of 0.25 ??M midday. Kinetic calculations show that the buildup of H2O2 is controlled by reaction with Fe(III), but this has only a small effect on Fe(II) because of the small formation rates of H2O2 compared to those of Fe(II). The results demonstrate the importance of incorporating the effects of light and dissolved organic carbon into Fe reactive transport models to further our understanding of the fate of Fe in streams and lakes.

Problems associated with using filtration to define dissolved trace element concentrations in natural water samples

USGS Publications Warehouse

Horowitz, A.J.; Lum, K.R.; Garbarino, J.R.; Hall, G.E.M.; Lemieux, C.; Demas, C.R.

1996-01-01

Field and laboratory experiments indicate that a number of factors associated with filtration other than just pore size (e.g., diameter, manufacturer, volume of sample processed, amount of suspended sediment in the sample) can produce significant variations in the 'dissolved' concentrations of such elements as Fe, Al, Cu, Zn, Pb, Co, and Ni. The bulk of these variations result from the inclusion/exclusion of colloidally associated trace elements in the filtrate, although dilution and sorption/desorption from filters also may be factors. Thus, dissolved trace element concentrations quantitated by analyzing filtrates generated by processing whole water through similar pore-sized filters may not be equal or comparable. As such, simple filtration of unspecified volumes of natural water through unspecified 0.45-??m membrane filters may no longer represent an acceptable operational definition for a number of dissolved chemical constituents.

Assessing element distribution and speciation in a stream at abandoned Pb-Zn mining site by combining classical, in-situ DGT and modelling approaches.

PubMed

Omanović, Dario; Pižeta, Ivanka; Vukosav, Petra; Kovács, Elza; Frančišković-Bilinski, Stanislav; Tamás, János

2015-04-01

The distribution and speciation of elements along a stream subjected to neutralised acid mine drainage (NAMD) effluent waters (Mátra Mountain, Hungary; Toka stream) were studied by a multi-methodological approach: dissolved and particulate fractions of elements were determined by HR-ICPMS, whereas speciation was carried out by DGT, supported by speciation modelling performed by Visual MINTEQ. Before the NAMD discharge, the Toka is considered as a pristine stream, with averages of dissolved concentrations of elements lower than world averages. A considerable increase of element concentrations caused by effluent water inflow is followed by a sharp or gradual concentration decrease. A large difference between total and dissolved concentrations was found for Fe, Al, Pb, Cu, Zn and As in effluent water and at the first downstream site, with high correlation factors between elements in particulate fraction, indicating their common behaviour, governed by the formation of ferri(hydr)oxides (co)precipitates. In-situ speciation by the DGT technique revealed that Zn, Cd, Ni, Co, Mn and U were predominantly present as a labile, potentially bioavailable fraction (>90%). The formation of strong complexes with dissolved organic matter (DOM) resulted in a relatively low DGT-labile concentration of Cu (42%), while low DGT-labile concentrations of Fe (5%) and Pb (12%) were presumably caused by their existence in colloidal (particulate) fraction which is not accessible to DGT. Except for Fe and Pb, a very good agreement between DGT-labile concentrations and those predicted by the applied speciation model was obtained, with an average correlation factor of 0.96. This study showed that the in-situ DGT technique in combination with model-predicted speciation and classical analysis of samples could provide a reasonable set of data for the assessment of the water quality status (WQS), as well as for the more general study of overall behaviour of the elements in natural waters subjected to high element loads. Copyright © 2014 Elsevier B.V. All rights reserved.

Two Reactive Zones within Riverbank Aquifers Impact the Accumulation of Arsenic within Permeable Natural Reactive Barrier

NASA Astrophysics Data System (ADS)

Knappett, P.; Myers, K.; Jewell, K.; Berube, M.; Datta, S.; Hossain, A.; Hosain, A.; Lipsi, M.; Ahmed, K. M.

2017-12-01

River stage fluctuations drives river water, rich oxidants, into riverbanks aquifers. When these aquifers are rich in dissolved iron (Fe), iron oxides (FeOOH) precipitate, creating a reactive surface upon which toxic elements such as arsenic (As) may sorb. These Permeable Natural Reactive Barriers (PNRBs) have been studied on the Meghna River. The lack of understanding of what controls their formation and fate could result in dangerous consequences. Pumping of riverbank aquifers for irrigation could re-mobilize toxic concentrations of As into drinking water aquifers. It is important to understand the hydrological, geochemical and biological processes controlling the properties of PNRBs. To this end, monitoring wells and drive-point piezometers were installed orthogonal to the Meghna River in Bangladesh. The dimensions of the shallow aquifer was mapped with Electrical Resistivity Tomography (ERT). The monitoring wells and a river gage were instrumented with pressure transducers to record water level fluctuations. Groundwater flows towards the river for most of the year but reverses under the influence of local irrigation pumping in the late dry season and rapidly rising river stage in the early monsoon. Semi-diurnal tides in the dry season have an amplitude of 80 cm. Declining concentrations of conservative dissolved ions towards the river indicated a zone of dilution from river water extending up to 50 m from the river's dry season edge. Dissolved As was produced as groundwater passed through this dilution zone until the final 20 m where As was abruptly removed from solution. This location coincided with a PNRB with enriched solid-phase Fe and Mn within the upper 3 m of sediment. 16S bacterial community DNA was sequenced from the wells and drive-point piezometers to map the distribution of Fe and As reducers and oxidizers. The richest overall biodiversity was found within the PNRB zone. It contained the most oxidizing and reducing species. This evidence suggests that transient river levels drive mixing between oxidizing and reducing agents in Hyporheic Zones (HZs). When the shallow aquifers are rich in dissolved concentrations of Fe and As, this mixing results in the accumulation of solid-phase Fe and As. This is likely a general process affecting other oxide-forming metals and toxic elements they bind.

Changing concentrations of CO, CH(4), C(5)H(8), CH(3)Br, CH(3)I, and dimethyl sulfide during the Southern Ocean Iron Enrichment Experiments.

PubMed

Wingenter, Oliver W; Haase, Karl B; Strutton, Peter; Friederich, Gernot; Meinardi, Simone; Blake, Donald R; Rowland, F Sherwood

2004-06-08

Oceanic iron (Fe) fertilization experiments have advanced the understanding of how Fe regulates biological productivity and air-sea carbon dioxide (CO(2)) exchange. However, little is known about the production and consumption of halocarbons and other gases as a result of Fe addition. Besides metabolizing inorganic carbon, marine microorganisms produce and consume many other trace gases. Several of these gases, which individually impact global climate, stratospheric ozone concentration, or local photochemistry, have not been previously quantified during an Fe-enrichment experiment. We describe results for selected dissolved trace gases including methane (CH(4)), isoprene (C(5)H(8)), methyl bromide (CH(3)Br), dimethyl sulfide, and oxygen (O(2)), which increased subsequent to Fe fertilization, and the associated decreases in concentrations of carbon monoxide (CO), methyl iodide (CH(3)I), and CO(2) observed during the Southern Ocean Iron Enrichment Experiments.

Analysis of total and dissolved heavy metals in surface water of a Mexican polluted river by total reflection X-ray fluorescence spectrometry

NASA Astrophysics Data System (ADS)

Zarazua, G.; Ávila-Pérez, P.; Tejeda, S.; Barcelo-Quintal, I.; Martínez, T.

2006-11-01

The present area of study is located in the Upper Course of the Lerma River (UCLR). The Lerma is one of the most important rivers of Mexico, where it drains highly populated and industrialized regions. The aim of the present study is to determine the heavy metal concentration of Cr, Mn, Fe, Cu and Pb in dissolved and total phases of the UCLR by means of Total Reflection X-ray Fluorescence Spectrometry (TXRF). The surface water samples were collected at 8 sites distributed following the stream flow direction of the river. Four sampling campaigns were carried out in each site in a 1-year period. A sample preparation method was applied in order to obtain the total and dissolved fraction and to destroy the organic matter. The total heavy metal average concentration decrease in the following order: Fe (2566 μg/L) > Mn (300 μg/L) > Cu (66 μg/L) > Cr (21 μg/L) > Pb (15 μg/L). In general, the heavy metal concentrations in water of the UCLR are below the maximum permissible limits.

Use of dissolved H2 concentrations to determine distribution of microbially catalyzed redox reactions in anoxic groundwater

USGS Publications Warehouse

Lovley, D.R.; Chapelle, F.H.; Woodward, J.C.

1994-01-01

The potential for using concentrations of dissolved H2 to determine the distribution of redox processes in anoxic groundwaters was evaluated. In pristine aquifers in which standard geochemical measurements indicated that Fe-(III) reduction, sulfate reduction, or methanogenesis was the terminal electron accepting process (TEAP), the H2 concentrations were similar to the H2 concentrations that have previously been reported for aquatic sediments with the same TEAPs. In two aquifers contaminated with petroleum products, it was impossible with standard geochemical analyses to determine which TEAPs predominated in specific locations. However, the TEAPs predicted from measurements of dissolved H2 were the same as those determined directly through measurements of microbial processes in incubated aquifer material. These results suggest that H2 concentrations may be a useful tool for analyzing the redox chemistry of nonequilibrium groundwaters.

Geochemical characterisation of shallow aquifer sediments of Matlab Upazila, Southeastern Bangladesh — Implications for targeting low-As aquifers

NASA Astrophysics Data System (ADS)

von Brömssen, Mattias; Häller Larsson, Sara; Bhattacharya, Prosun; Hasan, M. Aziz; Ahmed, Kazi Matin; Jakariya, M.; Sikder, Mohiuddin A.; Sracek, Ondra; Bivén, Annelie; Doušová, Barbora; Patriarca, Claudio; Thunvik, Roger; Jacks, Gunnar

2008-07-01

High arsenic (As) concentrations in groundwater pose a serious threat to the health of millions of people in Bangladesh. Reductive dissolution of Fe(III)-oxyhydroxides and release of its adsorbed As is considered to be the principal mechanism responsible for mobilisation of As. The distribution of As is extremely heterogeneous both laterally and vertically. Groundwater abstracted from oxidised reddish sediments, in contrast to greyish reducing sediments, contains significantly lower amount of dissolved arsenic and can be a source of safe water. In order to study the sustainability of that mitigation option, this study describes the lithofacies and genesis of the sediments within 60 m depth and establishes a relationship between aqueous and solid phase geochemistry. Oxalate extractable Fe and Mn contents are higher in the reduced unit than in the oxidised unit, where Fe and Mn are present in more crystalline mineral phases. Equilibrium modelling of saturation indices suggest that the concentrations of dissolved Fe, Mn and PO43--tot in groundwater is influenced by secondary mineral phases in addition to redox processes. Simulating AsIII adsorption on hydroferric oxides using the Diffuse Layer Model and analytical data gave realistic concentrations of dissolved and adsorbed AsIII for the reducing aquifer and we speculate that the presence of high PO43--tot in combination with reductive dissolution results in the high-As groundwater. The study confirms high mobility of As in reducing aquifers with typically dark colour of sediments found in previous studies and thus validates the approach for location of wells used by local drillers based on sediment colour. A more systematic and standardised colour description and similar studies at more locations are necessary for wider application of the approach.

Diel cycles in dissolved barium, lead, iron, vanadium, and nitrite in a stream draining a former zinc smelter site near Hegeler, Illinois

USGS Publications Warehouse

Kay, R.T.; Groschen, G.E.; Cygan, G.; Dupre, David H.

2011-01-01

Diel variations in the concentrations of a number of constituents have the potential to substantially affect the appropriate sampling regimen in acidic streams. Samples taken once during the course of the day cannot adequately reflect diel variations in water quality and may result in an inaccurate understanding of biogeochemical processes, ecological conditions, and of the threat posed by the water to human health and the associated wildlife. Surface water and groundwater affected by acid drainage were sampled every 60 to 90. min over a 48-hour period at a former zinc smelter known as the Hegeler Zinc Superfund Site, near Hegeler, Illinois. Diel variations related to water quality in the aquifer were not observed in groundwater. Diel variations were observed in the temperature, pH, and concentration of dissolved oxygen, nitrite, barium, iron, lead, vanadium, and possibly uranium in surface water. Temperature, dissolved oxygen, nitrite, barium, lead, and uranium generally attained maximum values during the afternoon and minimum values during the night. Iron, vanadium, and pH generally attained minimum values during the afternoon and maximum values during the night. Concentrations of dissolved oxygen were affected by the intensity of photosynthetic activity and respiration, which are dependent upon insolation. Nitrite, an intermediary in many nitrogen reactions, may have been formed by the oxidation of ammonium by dissolved oxygen and converted to other nitrogen species as part of the decomposition of organic matter. The timing of the pH cycles was distinctly different from the cycles found in Midwestern alkaline streams and likely was the result of the photoreduction of Fe3+ to Fe 2+ and variations in the intensity of precipitation of hydrous ferric oxide minerals. Diel cycles of iron and vanadium also were primarily the result of variations in the intensity of precipitation of hydrous ferric oxide minerals. The diel variation in the concentrations of lead, uranium, and barium may have been affected by competition with Fe+2 for sorption sites on hydrous ferric oxide minerals. ?? 2010.

A field, laboratory and modeling study of reactive transport of groundwater arsenic in a coastal aquifer

PubMed Central

Jung, Hun Bok; Charette, Matthew A.; Zheng, Yan

2009-01-01

A field, laboratory, and modeling study of As in groundwater discharging to Waquoit Bay, MA, shed light on coupled control of chemistry and hydrology on reactive transport of As in a coastal aquifer. Dissolved Fe(II) and As(III) in a reducing groundwater plume bracketed by an upper and a lower redox interface are oxidized as water flows towards the bay. This results in precipitation of Fe(III) oxides, along with oxidation and adsorption of As to sediment at the redox interfaces where concentrations of sedimentary HCl-leachable Fe (80~90% Fe(III)) are 734±232 mg kg-1, sedimentary phosphate extractable As (90~100% As(V)) are 316±111 μg kg-1, and are linearly correlated. Batch adsorption of As(III) onto orange, brown and gray sediments follows Langmuir isotherms, and can be fitted by a surface complexation model (SCM) assuming a diffuse layer for ferrihydrite. The sorption capacity and distribution coefficient for As increase with decreasing sediment Fe(II)/Fe. To allow accumulation of the amount of sediment As, similar hydrogeochemical conditions would have been operating for thousands of years at Waquoit Bay. The SCM simulated the observed dissolved As concentration better than a parametric approach based on Kd. Site specific isotherms should be established for Kd or SCM based models. PMID:19708362

Iron persistence in a distal hydrothermal plume supported by dissolved-particulate exchange

NASA Astrophysics Data System (ADS)

Fitzsimmons, Jessica N.; John, Seth G.; Marsay, Christopher M.; Hoffman, Colleen L.; Nicholas, Sarah L.; Toner, Brandy M.; German, Christopher R.; Sherrell, Robert M.

2017-02-01

Hydrothermally sourced dissolved metals have been recorded in all ocean basins. In the oceans' largest known hydrothermal plume, extending westwards across the Pacific from the Southern East Pacific Rise, dissolved iron and manganese were shown by the GEOTRACES program to be transported halfway across the Pacific. Here, we report that particulate iron and manganese in the same plume also exceed background concentrations, even 4,000 km from the vent source. Both dissolved and particulate iron deepen by more than 350 m relative to 3He--a non-reactive tracer of hydrothermal input--crossing isopycnals. Manganese shows no similar descent. Individual plume particle analyses indicate that particulate iron occurs within low-density organic matrices, consistent with its slow sinking rate of 5-10 m yr-1. Chemical speciation and isotopic composition analyses reveal that particulate iron consists of Fe(III) oxyhydroxides, whereas dissolved iron consists of nanoparticulate Fe(III) oxyhydroxides and an organically complexed iron phase. The descent of plume-dissolved iron is best explained by reversible exchange onto slowly sinking particles, probably mediated by organic compounds binding iron. We suggest that in ocean regimes with high particulate iron loadings, dissolved iron fluxes may depend on the balance between stabilization in the dissolved phase and the reversibility of exchange onto sinking particles.

Forms of trace arsenic, cesium, cadmium, and lead transported into river water for the irrigation of Japanese paddy rice fields

NASA Astrophysics Data System (ADS)

Nakaya, Shinji; Chi, Hai; Muroda, Kengo; Masuda, Harue

2018-06-01

In this study, we focus on the behavior of geogenic, toxic trace elements, particularly As, Cs, Cd, and Pb, during their transportation in two rivers for irrigation commonly used in monsoon Asia; one river originates from an active volcano, Mt. Asama, and the other originates from a currently inactive volcano, Yatsugatake Mountains in Nagano, Japan. These rivers were investigated to understand the role of river water as a pollutant of rice and other aquatic plants (via irrigation) and aquatic animals. The results indicated that the behavior of toxic trace elements in river water are likely controlled by their interactions with particulate Fe, Al, and Ti compounds. The majority of Pb and Cd is transported as particulate matter with Fe, Al, and Ti, while the majority of As is transported in the dissolved form, predominantly as arsenate, with low abundance of particulate matter. Cs is transported either as the dissolved form or as particulate matter in both rivers. The investigated elements are transported in the rivers as particulate and dissolved forms, and the ratio of these forms is controlled by the pH and presence of particulate Fe, Al, and Ti phases in the river water. With respect to Cs in both rivers, the parameter governing the concentration and transportation of Cs, in the bimodal form (i.e., particulate and dissolved forms), through the river possibly shifts from sorption to pH by particulate Fe-Al-Ti, according to the abrupt increase in the concentration of Cs in the river. The chemical attraction of particulate Fe-Al-Ti for Cs is weaker than that for Pb and Cd, indicating that the lower electronegativity of Cs weakens the chemical attraction on a colloid for the competitive sorption with the other trace elements. The different relationships between As and Fe in the river and in the irrigation water and soil water, as well as those in paddy rice, suggested that As in paddy rice is not directly derived from As in the irrigation water from the river under flooding.

DISSOLUTION OF PLUTONIUM METAL IN 8-10 M NITRIC ACID

DOE Office of Scientific and Technical Information (OSTI.GOV)

Rudisill, T. S.; Pierce, R. A.

2012-07-02

The H-Canyon facility will be used to dissolve Pu metal for subsequent purification and conversion to plutonium dioxide (PuO{sub 2}) using Phase II of HB-Line. To support the new mission, the development of a Pu metal dissolution flowsheet which utilizes concentrated (8-10 M) nitric acid (HNO{sub 3}) solutions containing potassium fluoride (KF) is required. Dissolution of Pu metal in concentrated HNO{sub 3} is desired to eliminate the need to adjust the solution acidity prior to purification by anion exchange. The preferred flowsheet would use 8-10 M HNO{sub 3}, 0.015-0.07 M KF, and 0.5-1.0 g/L Gd to dissolve the Pu upmore » to 6.75 g/L. An alternate flowsheet would use 8-10 M HNO{sub 3}, 0.05-0.2 M KF, and 1-2 g/L B to dissolve the Pu. The targeted average Pu metal dissolution rate is 20 mg/min-cm{sup 2}, which is sufficient to dissolve a “standard” 2250-g Pu metal button in 24 h. Plutonium metal dissolution rate measurements showed that if Gd is used as the nuclear poison, the optimum dissolution conditions occur in 10 M HNO{sub 3}, 0.04-0.05 M KF, and 0.5-1.0 g/L Gd at 112 to 116 °C (boiling). These conditions will result in an estimated Pu metal dissolution rate of ~11-15 mg/min-cm{sup 2} and will result in dissolution times of 36-48 h for standard buttons. The recommended minimum and maximum KF concentrations are 0.03 M and 0.07 M, respectively. The data also indicate that lower KF concentrations would yield dissolution rates for B comparable to those observed with Gd at the same HNO{sub 3} concentration and dissolution temperature. To confirm that the optimal conditions identified by the dissolution rate measurements can be used to dissolve Pu metal up to 6.75 g/L in the presence of representative concentrations of Fe and Gd or B, a series of experiments was performed to demonstrate the flowsheets. In three of the five experiments, the offgas generation rate during the dissolution was measured and samples were analyzed for hydrogen gas (H{sub 2}). The use of 10 M HNO{sub 3} containing 0.03-0.05 M KF, 0.5-1.0 g/L Gd, and 1.9 g/L Fe resulted in complete dissolution of the metal in 2.0-3.5 h. When B was used as the neutron poison, 10 M HNO{sub 3} solutions containing 0.05-0.1 M KF, 1.9 g/L Fe, and 1 g/L B resulted in complete dissolution of the metal in 0.75-2.0 h. Dissolution rates estimated using data from the flowsheet demonstrations agreed reasonably well with the measured rates; although, a discrepancy was observed in the Gd system. The presence of 1 g/L Gd or B in the dissolving solution had about the same effect on the dissolution rate. The predominant Pu valence in the dissolving solution was Pu(IV). The concentration of Pu(VI) was evaluated by UV-visible spectroscopy and was estimated to be significantly less than 1 wt %. The offgas generation rates and H{sub 2} concentrations measured in the offgas from experiments performed using 10 M HNO{sub 3} containing 0.05 M KF, 1.9 g/L Fe and either 1 g/L Gd or B were approximately the same. These data support the conclusion that the presence of either 1 g/L Gd or B had the same general effect on the dissolution rate. The calculated offgas generation during the dissolutions was 0.6 mol offgas/mol of Pu. The H{sub 2} concentration measured in the offgas from the dissolution using Gd as the neutron poison was approximately 0.5 vol %. In the B system, the H{sub 2} ranged from nominally 0.8 to 1 vol % which is about the same as measured in the Gd system within the uncertainty of the analysis. The offgas generation rate for the dissolution performed using 10 M HNO{sub 3} containing 0.03 M KF, 0.5 g/L Gd, and 1.9 g/L Fe was approximately a factor of two less than produced in the other dissolutions; however, the concentration of H{sub 2} measured in the offgas was higher. The adjusted concentration ranged from 2.7 to 8.8 vol % as the dissolution proceeded. Higher concentrations of H{sub 2} occur when the Pu dissolution proceeds by a metal/acid reaction rather than nitrate oxidation. The higher H{sub 2} concentration could be attributed to the reduced activity of the fluoride due to complexation with Pu as the dissolution progressed. Dissolution of Pu metal at 20 °C in 10 M HNO{sub 3} containing 0.05 M KF showed that the Pu metal dissolves slowly without any visible gas generation. As the Pu metal dissolves, it forms a more-dense Pu-bearing solution which sank to the bottom of the dissolution vessel. The dissolved Pu did not form a boundary layer around the sample and failed to distribute homogeneously due to minimal (thermally-induced) mixing. This indicates that in the H-Canyon dissolver insert, the Pu will diffuse out of the insert into the bulk dissolver solution where it will disperse. At 35 °C, the Pu metal dissolved without visible gas generation. However, due to thermal currents caused by maintaining the solution at 35 °C, the dissolved Pu distributed evenly throughout the dissolver solution. It did not form a boundary layer around the sample.« less

Dissolved and particulate trace metal micronutrients under the McMurdo Sound seasonal sea ice: basal sea ice communities as a capacitor for iron

PubMed Central

Noble, Abigail E.; Moran, Dawn M.; Allen, Andrew E.; Saito, Mak A.

2013-01-01

Dissolved and particulate metal concentrations are reported from three sites beneath and at the base of the McMurdo Sound seasonal sea ice in the Ross Sea of Antarctica. This dataset provided insight into Co and Mn biogeochemistry, supporting a previous hypothesis for water column mixing occurring faster than scavenging. Three observations support this: first, Mn-containing particles with Mn/Al ratios in excess of the sediment were present in the water column, implying the presence of bacterial Mn-oxidation processes. Second, dissolved and labile Co were uniform with depth beneath the sea ice after the winter season. Third, dissolved Co:PO3−4 ratios were consistent with previously observed Ross Sea stoichiometry, implying that over-winter scavenging was slow relative to mixing. Abundant dissolved Fe and Mn were consistent with a winter reserve concept, and particulate Al, Fe, Mn, and Co covaried, implying that these metals behaved similarly. Elevated particulate metals were observed in proximity to the nearby Islands, with particulate Fe/Al ratios similar to that of nearby sediment, consistent with a sediment resuspension source. Dissolved and particulate metals were elevated at the shallowest depths (particularly Fe) with elevated particulate P/Al and Fe/Al ratios in excess of sediments, demonstrating a sea ice biomass source. The sea ice biomass was extremely dense (chl a >9500 μg/L) and contained high abundances of particulate metals with elevated metal/Al ratios. A hypothesis for seasonal accumulation of bioactive metals at the base of the McMurdo Sound sea ice by the basal algal community is presented, analogous to a capacitor that accumulates iron during the spring and early summer. The release and transport of particulate metals accumulated at the base of the sea ice by sloughing is discussed as a potentially important mechanism in providing iron nutrition during polynya phytoplankton bloom formation and could be examined in future oceanographic expeditions. PMID:24790953

Dissolved and particulate trace metal micronutrients under the McMurdo Sound seasonal sea ice: basal sea ice communities as a capacitor for iron

NASA Astrophysics Data System (ADS)

Noble, Abigail; Saito, Mak; Moran, Dawn; Allen, Andrew

2013-10-01

Dissolved and particulate metal concentrations are reported from three sites beneath and at the base of the McMurdo Sound seasonal sea ice in the Ross Sea of Antarctica. This dataset provided insight into Co and Mn biogeochemistry, supporting a previous hypothesis for water column mixing occurring faster than scavenging. Three observations support this: first, Mn-containing particles with Mn/Al ratios in excess of the sediment were present in the water column, implying the presence of bacterial Mn-oxidation processes. Second, dissolved and labile Co were uniform with depth beneath the sea ice after the winter season. Third, dissolved Co:PO43- ratios were consistent with previously observed Ross Sea stoichiometry, implying that over-winter scavenging was slow relative to mixing. Abundant dissolved Fe and Mn were consistent with a winter reserve concept, and particulate Al, Fe, Mn, and Co covaried, implying that these metals behaved similarly. Elevated particulate metals were observed in proximity to the nearby Islands, with particulate Fe/Al ratios similar to that of nearby sediment, consistent with a sediment resuspension source. Dissolved and particulate metals were elevated at the shallowest depths (particularly Fe) with elevated particulate P/Al and Fe/Al ratios in excess of sediments, demonstrating a sea ice biomass source. The sea ice biomass was extremely dense (chl a >9500 μg/L) and contained high abundances of particulate metals with elevated metal/Al ratios. A hypothesis for seasonal accumulation of bioactive metals at the base of the McMurdo Sound sea ice by the basal algal community is presented, analogous to a capacitor that accumulates iron during the spring and early summer. The release and transport of particulate metals accumulated at the base of the sea ice by sloughing is discussed as a potentially important mechanism in providing iron nutrition during polynya phytoplankton bloom formation and could be examined in future oceanographic expeditions.

Effects of carbonate species on the kinetics of dechlorination of 1,1,1-trichloroethane by zero-valent iron.

PubMed

Agrawal, Abinash; Ferguson, William J; Gardner, Bruce O; Christ, John A; Bandstra, Joel Z; Tratnyek, Paul G

2002-10-15

The effect of precipitates on the reactivity of iron metal (Fe0) with 1,1,1-trichloroethane (TCA) was studied in batch systems designed to model groundwaters that contain dissolved carbonate species (i.e., C(IV)). At representative concentrations for high-C(IV) groundwaters (approximately 10(-2) M), the pH in batch reactors containing Fe0 was effectively buffered until most of the aqueous C(IV) precipitated. The precipitate was mainly FeCO3 (siderite) but may also have included some carbonate green rust. Exposure of the Fe0 to dissolved C(IV) accelerated reduction of TCA, and the products formed under these conditions consisted mainly of ethane and ethene, with minor amounts of several butenes. The kinetics of TCA reduction were first-order when C(IV)-enhanced corrosion predominated but showed mixed-order kinetics (zero- and first-order) in experiments performed with passivated Fe0 (i.e., before the onset of pitting corrosion and after repassivation by precipitation of FeCO3). All these data were described by fitting a Michaelis-Menten-type kinetic model and approximating the first-order rate constant as the ratio of the maximum reaction rate (Vm) and the concentration of TCA at half of the maximum rate (K(1/2)). The decrease in Vm/K(1/2) with increasing C(IV) exposure time was fit to a heuristic model assuming proportionality between changes in TCA reduction rate and changes in surface coverage with FeCO3.

Mn cycling in marine biofilms: effect on the rate of localized corrosion.

PubMed

Dexter, S C; Xu, K; Luther, G L

2003-04-01

Microelectrodes of the Au-Hg amalgam type have been used together with square wave voltammetry to measure profiles of oxygen, peroxide, Fe, Mn and sulfur chemical species through the thickness of natural assemblage marine biofilms grown on stainless steel alloy Nitronic 50 (UNS S20910). The data show Mn+2 and peroxide together at locations where the dissolved oxygen concentration was low. Oxidized species of Fe were also found at some locations. Sulfur species (predominantly S-2) was often found at locations where the dissolved oxygen concentration was below the detectable limit. Confocal scanning laser microscopy was used to image the microbial assemblage at the locations of the chemical profile data. Organisms with a filamentous morphology were found in consortia with rod and coccoidal shaped microbes at locations where dissolved Mn and peroxide were measured. The filamentous forms were usually absent at locations where Mn was not detected. It is suggested that the filamentous organisms may be Mn metabolizers, and that peroxidatic Mn re-oxidation may be taking place within the biofilm.

Growth, Toxin Production and Allelopathic Effects of Pseudo-nitzschia multiseries under Iron-Enriched Conditions

PubMed Central

Sobrinho, Bruna Fernanda; de Camargo, Luana Mocelin; Sandrini-Neto, Leonardo; Kleemann, Cristian Rafael; Machado, Eunice da Costa; Mafra, Luiz Laureno

2017-01-01

In order to assess the effects of Fe-enrichment on the growth and domoic acid (DA) production of the toxigenic diatom Pseudo-nitzschia multiseries, static cultures that received the addition of different iron (Fe) concentrations were maintained for 30 days. Intra- and extracellular DA concentrations were evaluated over time, and growth and chain-formation were compared to those of non-toxic diatoms, Bacillaria sp. Growth rates of P. multiseries (μ = 0.45–0.73 d−1) were similar among cultures containing different Fe concentrations. Likewise, the similar incidence and length of P. multiseries stepped cell chains (usually 2–4; up to 8-cell long) among the treatments reinforces that the cultures were not growth-inhibited under any condition tested, suggesting an efficient Fe acquisition mechanism. Moreover, DA concentrations were significantly higher under the highest Fe concentration, indicating that Fe is required for toxin synthesis. Bacillaria sp. reached comparable growth rates under the same Fe concentrations, except when the dissolved cell contents from a P. multiseries culture was added. The 50–70% reduction in cell density and 70–90% decrease in total chlorophyll-a content of Bacillaria sp. at early stationary growth phase indicates, for the first time, an allelopathic effect of undetermined compounds released by Pseudo-nitzschia to another diatom species. PMID:29064395

Growth, Toxin Production and Allelopathic Effects of Pseudo-nitzschia multiseries under Iron-Enriched Conditions.

PubMed

Sobrinho, Bruna Fernanda; de Camargo, Luana Mocelin; Sandrini-Neto, Leonardo; Kleemann, Cristian Rafael; Machado, Eunice da Costa; Mafra, Luiz Laureno

2017-10-24

In order to assess the effects of Fe-enrichment on the growth and domoic acid (DA) production of the toxigenic diatom Pseudo-nitzschia multiseries , static cultures that received the addition of different iron (Fe) concentrations were maintained for 30 days. Intra- and extracellular DA concentrations were evaluated over time, and growth and chain-formation were compared to those of non-toxic diatoms, Bacillaria sp. Growth rates of P. multiseries (μ = 0.45-0.73 d -1 ) were similar among cultures containing different Fe concentrations. Likewise, the similar incidence and length of P. multiseries stepped cell chains (usually 2-4; up to 8-cell long) among the treatments reinforces that the cultures were not growth-inhibited under any condition tested, suggesting an efficient Fe acquisition mechanism. Moreover, DA concentrations were significantly higher under the highest Fe concentration, indicating that Fe is required for toxin synthesis. Bacillaria sp. reached comparable growth rates under the same Fe concentrations, except when the dissolved cell contents from a P. multiseries culture was added. The 50-70% reduction in cell density and 70-90% decrease in total chlorophyll-a content of Bacillaria sp. at early stationary growth phase indicates, for the first time, an allelopathic effect of undetermined compounds released by Pseudo-nitzschia to another diatom species.

Diurnal variations in, and influences on, concentrations of particulate and dissolved arsenic and metals in the mildly alkaline Wallkill River, New Jersey, USA

NASA Astrophysics Data System (ADS)

Barringer, Julia L.; Wilson, Timothy P.; Szabo, Zoltan; Bonin, Jennifer L.; Fischer, Jeffrey M.; Smith, Nicholas P.

2008-01-01

Diurnal variations in particulate and dissolved As and metal concentrations were observed in mildly alkaline water from a wetlands site on the Wallkill River in northwestern New Jersey. The site, underlain by glacial sediments over dolomite bedrock, is 10 km downstream from a mined area of the Franklin Marble, host to Zn ores, also As and Mn minerals. In mid-September 2005, maxima and minima in dissolved-oxygen-concentration and pH, typically caused by photosynthesis and respiration, occurred at 2000 and 0800 hours. Concentrations of dissolved As (1.52-1.95 μg/L) peaked at dusk (2000 hours), whereas dissolved Mn and Zn concentrations (76.5-96.9 and 8.55-12.8 μg/L, respectively) were lowest at dusk and peaked at 1000 hours. These opposing cycles probably reflect sorption and desorption of As (an anion), and Mn and Zn (cations) as pH varied throughout the 24-h period. Doubly-peaked cycles of B, Cl, SO4, and nutrients also were observed; these may result from upstream discharges of septic-system effluent. Both recoverable amd particulate Al, Fe, Mn, and Zn concentrations peaked between 0200 and 0600 hours. The particulate metals cycle, with perturbations at 0400 hours, may be influenced by biological activity.

Remediation of arsenic-contaminated groundwater by in-situ stimulating biogenic precipitation of iron sulfides.

PubMed

Pi, Kunfu; Wang, Yanxin; Xie, Xianjun; Ma, Teng; Liu, Yaqing; Su, Chunli; Zhu, Yapeng; Wang, Zhiqiang

2017-02-01

Severe health problems due to elevated arsenic (As) in groundwater have made it urgent to develop cost-effective technologies for As removal. This field experimental study tested the feasibility of in-situ As immobilization via As incorporation into newly formed biogenic Fe(II) sulfides in a typical As-affected strongly reducing aquifer at the central part of Datong Basin, China. After periodic supply of FeSO 4 into the aquifer for 25 d to stimulate microbial sulfate reduction, dissolved sulfide concentrations increased during the experiment, but the supplied Fe(II) reacted quickly with sulfide to form Fe(II)-sulfides existing majorly as mackinawite as well as a small amount of pyrite-like minerals in sediments, thereby restricting sulfide build-up in groundwater. After the completion of field experiment, groundwater As concentration decreased from an initial average value of 593 μg/L to 159 μg/L, with an overall As removal rate of 73%, and it further declined to 136 μg/L adding the removal rate up to 77% in 30 d after the experiment. The arsenite/As total ratio gradually increased over time, making arsenite to be the predominant species in groundwater residual As. The good correlations between dissolved Fe(II), sulfide and As concentrations, the increased abundance of As in newly-formed Fe sulfides as well as the reactive-transport modeling results all indicate that As could have been adsorbed onto and co-precipitated with Fe(II)-sulfide coatings once microbial sulfate reduction was stimulated after FeSO 4 supply. Under the strongly reducing conditions, sulfide may facilitate arsenate reduction into arsenite and promote As incorporation into pyrite or arsenopyrite. Therefore, the major mechanisms for the in-situ As-contaminated groundwater remediation can be As surface-adsorption on and co-precipitation with Fe(II) sulfides produced during the experimental period. Copyright © 2016. Published by Elsevier Ltd.

Precise measurement of Fe isotopes in marine samples by multi-collector inductively coupled plasma mass spectrometry (MC-ICP-MS).

PubMed

de Jong, Jeroen; Schoemann, Véronique; Tison, Jean-Louis; Becquevort, Sylvie; Masson, Florence; Lannuzel, Delphine; Petit, Jérôme; Chou, Lei; Weis, Dominique; Mattielli, Nadine

2007-04-18

A novel analytical technique for isotopic analysis of dissolved and particulate iron (Fe) from various marine environments is presented in this paper. It combines coprecipitation of dissolved Fe (DFe) samples with Mg(OH)(2), and acid digestion of particulate Fe (PFe) samples with double pass chromatographic separation. Isotopic data were obtained using a Nu Plasma MC-ICP-MS in dry plasma mode, applying a combination of standard-sample bracketing and external normalization by Cu doping. Argon interferences were determined prior to each analysis and automatically subtracted during analysis. Sample size can be varied between 200 and 600 ng of Fe per measurement and total procedural blanks are better than 10 ng of Fe. Typical external precision of replicate analyses (1S.D.) is +/-0.07 per thousand on delta(56)Fe and +/-0.09 per thousand on delta(57)Fe while typical internal precision of a measurement (1S.E.) is +/-0.03 per thousand on delta(56)Fe and +/-0.04 per thousand on delta(57)Fe. Accuracy and precision were assured by the analysis of reference material IRMM-014, an in-house pure Fe standard, an in-house rock standard, as well as by inter-laboratory comparison using a hematite standard from ETH (Zürich). The lowest amount of Fe (200 ng) at which a reliable isotopic measurement could still be performed corresponds to a DFe or PFe concentration of approximately 2 nmol L(-1) for a 2 L sample size. To show the versatility of the method, results are presented from contrasting environments characterized by a wide range of Fe concentrations as well as varying salt content: the Scheldt estuary, the North Sea, and Antarctic pack ice. The range of DFe and PFe concentrations encountered in this investigation falls between 2 and 2000 nmol L(-1) Fe. The distinct isotopic compositions detected in these environments cover the whole range reported in previous studies of natural Fe isotopic fractionation in the marine environment, i.e. delta(56)Fe varies between -3.5 per thousand and +1.5 per thousand. The largest fractionations were observed in environments characterized by redox changes and/or strong Fe cycling. This demonstrates the potential use of Fe isotopes as a tool to trace marine biogeochemical processes involving Fe.

Element ratios between digestive gland and gill tissues of the Antarctic bivalve Laternula elliptica as a proxy for element uptake from different environmental sources

NASA Astrophysics Data System (ADS)

Poigner, H.; Monien, D.; Monien, P.; Kriews, M.; Brumsack, H.-J.; Wilhelms-Dick, D.; Abele, D.

2012-04-01

Trace metals in bivalve carbonate shells are frequently used as environmental or paleoclimate proxies. Carbonate mineralogy and animals' physiology affect the incorporation of elements from different environmental sources into bivalve shells. Generally, metals from particulate matter are assimilated via the digestive tract; whereas dissolved metals are absorbed via gills. Therefore, measurements of element concentrations deposited in the shell matrix do not necessarily allow inference with respect to the assimilation pathways. In this study, we used element ratios between digestive gland (DG) and gills (cDG/cGill) of the Circum-Antarctic clam Laternula elliptica to identify predominating assimilation pathways and potential sources of bio-available metals. This normalization between tissues of each individual eliminates the effects of individual age and physiological condition (e.g. accumulation over lifetime, metabolic activity) on metal assimilation. These effects also minimize the reproducibility, when absolute element concentrations are compared between individuals from different locations. Therefore, an additional normalization is required. We favored "ellipsoid shell volume" over shell length or soft tissue weight as more conservative approximation for intra- and intersite comparisons. Metal concentrations in DG, gills, and hemolymph of the bivalve L. elliptica, collected at Potter Cove (King George Island, Antarctic Peninsula), were analyzed by means of inductively coupled plasma - optical emission spectroscopy and mass spectrometry after total acid digestion. The element ratios (cDG/cGill) indicate a predominant assimilation of Al, Ca, Fe, K, Mn, and Mg from the dissolved phase. These high Al and Fe concentrations in gill tissues and hemolymph are in contrast to the low solubility of Al and Fe in seawater. But high dissolved Fe concentrations in pore waters (up to 1400 μg L-1 due to suboxic sediment conditions) and glacial melt waters enriched in dissolved Al (of approx. 54 μg L-1 due to weathering processes) with respect to seawater concentrations (5.4-13.5 μg L-1) are likely bio-available sources at Potter Cove. In contrast, Cd, Cu, and Sr are mainly assimilated via the digestion of particulates. Since most studies on metal incorporation into bivalve shells have provided mathematical correlations to environmental data, this proxy-based approach provides a more causal relationship between sources and assimilation pathways. It improves the interpretation of element variations (if independent from shell mineralogy) in bivalve shells, especially, where a full characterization of the biogeochemical environment of the bivalves is lacking.

Development of copper recovery process from flotation tailings by a combined method of high‒pressure leaching‒solvent extraction.

PubMed

Han, Baisui; Altansukh, Batnasan; Haga, Kazutoshi; Stevanović, Zoran; Jonović, Radojka; Avramović, Ljiljana; Urosević, Daniela; Takasaki, Yasushi; Masuda, Nobuyuki; Ishiyama, Daizo; Shibayama, Atsushi

2018-06-15

Sulfide copper mineral, typically Chalcopyrite (CuFeS 2 ), is one of the most common minerals for producing metallic copper via the pyrometallurgical process. Generally, flotation tailings are produced as a byproduct of flotation and still consist of un‒recovered copper. In addition, it is expected that more tailings will be produced in the coming years due to the increased exploration of low‒grade copper ores. Therefore, this research aims to develop a copper recovery process from flotation tailings using high‒pressure leaching (HPL) followed by solvent extraction. Over 94.4% copper was dissolved from the sample (CuFeS 2 as main copper mineral) by HPL in a H 2 O media in the presence of pyrite, whereas the iron was co‒dissolved with copper according to an equation given as C Cu  = 38.40 × C Fe . To avoid co‒dissolved iron giving a negative effect on the subsequent process of electrowinning, solvent extraction was conducted on the pregnant leach solution for improving copper concentration. The result showed that 91.3% copper was recovered in a stripped solution and 98.6% iron was removed under the optimal extraction conditions. As a result, 86.2% of copper was recovered from the concentrate of flotation tailings by a proposed HPL‒solvent extraction process. Copyright © 2018 Elsevier B.V. All rights reserved.

Pyrite oxidation in the presence of hematite and alumina: I. Batch leaching experiments and kinetic modeling calculations.

PubMed

Tabelin, Carlito Baltazar; Veerawattananun, Suchol; Ito, Mayumi; Hiroyoshi, Naoki; Igarashi, Toshifumi

2017-02-15

Pyrite is one of the most common and geochemically important sulfide minerals in nature because of its role in the redox recycling of iron (Fe). It is also the primary cause of acid mine drainage (AMD) that is considered as a serious and widespread problem facing the mining and mineral processing industries. In the environment, pyrite oxidation occurs in the presence of ubiquitous metal oxides, but the roles that they play in this process remain largely unknown. This study evaluates the effects of hematite (α-Fe 2 O 3 ) and alumina (α-Al 2 O 3 ) on pyrite oxidation by batch-reactor type experiments, surface-sensitive characterization of the oxidation layer and thermodynamic/kinetic modeling calculations. In the presence of hematite, dissolved sulfur (S) concentration dramatically decreased independent of the pH, and the formation of intermediate sulfoxy anionic species on the surface of pyrite was retarded. These results indicate that hematite minimized the overall extent of pyrite oxidation, but the kinetic model could not explain how this suppression occurred. In contrast, pyrite oxidation was enhanced in the alumina suspension as suggested by the higher dissolved S concentration and stronger infrared (IR) absorption bands of surface-bound oxidation products. Based on the kinetic model, alumina enhanced the oxidative dissolution of pyrite because of its strong acid buffering capacity, which increased the suspension pH. The higher pH values increased the oxidation of Fe 2+ to Fe 3+ by dissolved O 2 (DO) that enhanced the overall oxidative dissolution kinetics of pyrite. Copyright © 2016 Elsevier B.V. All rights reserved.

Water-chemistry data for selected springs, geysers, and streams in Yellowstone National Park, Wyoming, 1999-2000

USGS Publications Warehouse

Ball, James W.; McCleskey, R. Blaine; Nordstrom, D. Kirk; Holloway, JoAnn M.; Verplanck, Philip L.; Sturtevant, Sabin A.

2002-01-01

Sixty-seven water analyses are reported for samples collected from 44 hot springs and their overflow drainages and two ambient-temperature acid streams in Yellowstone National Park (YNP) during 1990-2000. Thirty-seven analyses are reported for 1999, 18 for June of 2000, and 12 for September of 2000. These water samples were collected and analyzed as part of research investigations in YNP on microbially mediated sulfur oxidation in stream water, arsenic and sulfur redox speciation in hot springs, and chemical changes in overflow drainages that affect major ions, redox species, and trace elements. Most samples were collected from sources in the Norris Geyser Basin. Two ambient-temperature acidic stream systems, Alluvium and Columbine Creeks and their tributaries in Brimstone Basin, were studied in detail. Analyses were performed at or near the sampling site, in an on-site mobile laboratory truck, or later in a USGS laboratory, depending on stability of the constituent and whether or not it could be preserved effectively. Water temperature, specific conductance, pH, Eh, dissolved oxygen (D.O.), and dissolved H2S were determined on-site at the time of sampling. Alkalinity, acidity, and F were determined within a few days of sample collection by titration with acid, titration with base, and ion-selective electrode or ion chromatography (IC), respectively. Concentrations of S2O3 and SxO6 were determined as soon as possible (minutes to hours later) by IC. Concentrations of Br, Cl, NH4, NO2, NO3, SO4, Fe(II), and Fe(total) were determined within a few days of sample collection. Densities were determined later in the USGS laboratory. Concentrations of Li and K were determined by flame atomic absorption spectrometry. Concentrations of Al, As(total), B, Ba, Be, Ca, Cd, Co, Cr, Cu, Fe(total), K, Li, Mg, Mn, Na, Ni, Pb, Se, Si, Sr, V, and Zn were determined by inductively-coupled plasma-optical emission spectrometry. Trace concentrations of Cd, Cr, Cu, Pb, and Sb were determined by Zeeman-corrected graphitefurnace atomic-absorption spectrometry. Trace concentrations of As(total) and As(III) were determined by hydride generation atomic-absorption spectrometry using a flow-injection analysis system. Concentrations of Cl, NO3, Br, and SO4 were determined by IC. Concentrations of Fe(II) and Fe(total) were determined by the ferrozine colorimetric method. Concentrations of NO2 were determined by colorimetry using matrix-matched standards. Concentrations of NH4 were determined by IC, with reanalysis by colorimetry where separation of Na and NH4 peaks was poor. Dissolved organic carbon (DOC) concentrations were determined by the wet persulfate oxidation method.

The Effect of the Concentration of Oxidant, Cr(VI), on the Iron Oxidation in Saline Water

NASA Astrophysics Data System (ADS)

Ahn, H.; Jo, H. Y.; Ryu, J. H.; Koh, Y. K.

2014-12-01

Deep geological disposal is currently considered as the most appropriate method to isolate high level radioactive wastes (HLRWs) from the ecosystem. If groundwater seeps into underground disposal facilities, water molecules can be dissociated to radicals or peroxides, which can oxidize metal canisters and HLRWs. The oxidized radionuclides with a high solubility can be dissolved in the groundwater. Some dissolved radionuclides can act as oxidants. The continuous radiolysis of water molecules, which results from continuous seepage of groundwater, can enable the continuous production of the radioactive oxidants, resulting in an increase in concentration of oxidants. In this study, the effect of oxidant concentration on iron oxidation in the presence of salt was evaluated. Zero valent iron (ZVI) particles were reacted with Cr(VI) solutions with initial Cr(VI) concentrations ranged from 50 to 300 mg/L in reactors. The initial pH and NaCl concentration were fixed at 3 and 0.5 M, respectively. An increase in the initial Cr(VI) concentration caused an increase in the rate and extend of H2 gas production. The decrement of Cr(VI) was increased as the initial Cr(VI) concentration was increased. The penetration of H+ ions in the presence Cl- ions through the passive film on the ZVI particles caused the reaction between H+ ions and ZVI particles, producing H2 gas and Fe2+ ions. The passive film was damaged during the reaction due to the eruption of H2 gas or peptization by Cl- ions. The Fe2+ ions were reacted with Cr(VI) ions in the solution, producing Fe(III)-Cr(III) (oxy)hydroxides on the passive film of ZVI particles or in the solution as colloidal particles. The Fe(III)-Cr(III) (oxy)hydroxides tends to be precipitated as colloidal particles at a high Cr(VI) concentration and precipitated on the passive film at a low Cr(VI) concentration. The passive film was repaired or thickened by additional formation of Fe(III)-Cr(III) (oxy)hydroxides at a lower Cr(VI) concentration.

Calcium carbonate-based permeable reactive barriers for iron and manganese groundwater remediation at landfills.

PubMed

Wang, Yu; Pleasant, Saraya; Jain, Pradeep; Powell, Jon; Townsend, Timothy

2016-07-01

High concentrations of iron (Fe(II)) and manganese (Mn(II)) reductively dissolved from soil minerals have been detected in groundwater monitoring wells near many municipal solid waste landfills. Two in situ permeable reactive barriers (PRBs), comprised of limestone and crushed concrete, were installed downgradient of a closed, unlined landfill in Florida, USA, to remediate groundwater containing high concentrations of these metals. Influent groundwater to the PRBs contained mean Fe and Mn concentrations of approximately 30mg/L and 1.62mg/L, respectively. PRBs were constructed in the shallow aquifer (maximum depth 4.6m below land surface) and groundwater was sampled from a network of nearby monitoring wells to evaluate barrier performance in removing these metals. PRBs significantly (p<0.05) removed dissolved Fe and Mn from influent groundwater; Fe was removed from influent water at average rates of 91% and 95% (by mass) for the limestone and crushed concrete PRBs, respectively, during the first year of the study. The performance of the PRBs declined after 3years of operation, with Fe removal efficiency decreasing to 64% and 61% for limestone and concrete PRBs, respectively. A comparison of water quality in shallow and deep monitoring wells showed a more dramatic performance reduction in the deeper section of the concrete PRB, which was attributed to an influx of sediment into the barrier and settling of particulates from the upper portions of the PRBs. Although removal of Fe and Mn from redox impacts was achieved with the PRBs, the short time frame of effectiveness relative to the duration of a full-scale remediation effort may limit the applicability of these systems at some landfills because of the construction costs required. Copyright © 2016 Elsevier Ltd. All rights reserved.

Rates of arsenopyrite oxidation by oxygen and Fe(III) at pH 1.8-12.6 and 15-45 degrees C.

PubMed

Yu, Yunmei; Zhu, Yongxuan; Gao, Zhenmin; Gammons, Christopher H; Li, Denxian

2007-09-15

The oxidation rate of arsenopyrite by dissolved oxygen was measured using a mixed flow reactor at dissolved O2 concentrations of 0.007-0.77 mM, pH 1.8-12.6, and temperatures of 15-45 degrees C. As(III) was the dominant redox species (>75%) in the experimental system, and the As(III)/As(V) ratio of effluent waters did not change with pH. The results were used to derive the following rate law expression (valid between pH 1.8 and 6.4): r = 10((-2211 +/- 57)T) (mO2)(0.45 +/- 0.05), where r is the rate of release of dissolved As in mol m(-2) s(-1) and T is in Kelvin. Activation energies (Ea) for oxidation of arsenopyrite by 02 at pH 1.8 and 5.9 are 43 and 57 kJ/mol, respectively, and they compare to an Ea value of 16 kJ/mol for oxidation by Fe(III) at pH 1.8. Apparent As release rates passed through a minimum in the pH range 7-8, which may have been due to oxidation of Fe2+ to hydrous ferric oxide (HFO) with attenuation of dissolved As onto the freshly precipitated HFO.

Fractionation of fulvic acid by iron and aluminum oxides: influence on copper toxicity to Ceriodaphnia dubia

USGS Publications Warehouse

Smith, Kathleen S.; Ranville, James F.; Lesher, Emily K.; Diedrich, Daniel J.; McKnight, Diane M.; Sofield, Ruth M.

2014-01-01

This study examines the effect on aquatic copper toxicity of the chemical fractionation of fulvic acid (FA) that results from its association with iron and aluminum oxyhydroxide precipitates. Fractionated and unfractionated FAs obtained from streamwater and suspended sediment were utilized in acute Cu toxicity tests on ,i>Ceriodaphnia dubia. Toxicity test results with equal FA concentrations (6 mg FA/L) show that the fractionated dissolved FA was 3 times less effective at reducing Cu toxicity (EC50 13 ± 0.6 μg Cu/L) than were the unfractionated dissolved FAs (EC50 39 ± 0.4 and 41 ± 1.2 μg Cu/L). The fractionation is a consequence of preferential sorption of molecules having strong metal-binding (more aromatic) moieties to precipitating Fe- and Al-rich oxyhydroxides, causing the remaining dissolved FA to be depleted in these functional groups. As a result, there is more bioavailable dissolved Cu in the water and hence greater potential for Cu toxicity to aquatic organisms. In predicting Cu toxicity, biotic ligand models (BLMs) take into account dissolved organic carbon (DOC) concentration; however, unless DOC characteristics are accounted for, model predictions can underestimate acute Cu toxicity for water containing fractionated dissolved FA. This may have implications for water-quality criteria in systems containing Fe- and Al-rich sediment, and in mined and mineralized areas in particular. Optical measurements, such as specific ultraviolet absorbance at 254 nm (SUVA254), show promise for use as spectral indicators of DOC chemical fractionation and inferred increased Cu toxicity.

Magnesium transport extraction of transuranium elements from LWR fuel

DOEpatents

Ackerman, John P.; Battles, James E.; Johnson, Terry R.; Miller, William E.; Pierce, R. Dean

1992-01-01

A process of separating transuranium actinide values from uranium values present in spent nuclear oxide fuels which contain rare earth and noble metal fission products. The oxide fuel is reduced with Ca metal in the presence of CaCl.sub.2 and a U-Fe alloy containing not less than about 84% by weight uranium at a temperature in the range of from about 800.degree. C. to about 850.degree. C. to produce additional uranium metal which dissolves in the U-Fe alloy raising the uranium concentration and having transuranium actinide metals and rare earth fission product metals and the noble metal fission products dissolved therein. The CaCl.sub.2 having CaO and fission products of alkali metals and the alkali earth metals and iodine dissolved therein is separated and electrolytically treated with a carbon electrode to reduce the CaO to Ca metal while converting the carbon electrode to CO and CO.sub.2. The Ca metal and CaCl.sub.2 is recycled to reduce additional oxide fuel. The U-Fe alloy having transuranium actinide metals and rare earth fission product metals and the noble metal fission products dissolved therein is contacted with Mg metal which takes up the actinide and rare earth fission product metals. The U-Fe alloy retains the noble metal fission products and is stored while the Mg is distilled and recycled leaving the transuranium actinide and rare earth fission products isolated.

Iron release from corroded iron pipes in drinking water distribution systems: effect of dissolved oxygen.

PubMed

Sarin, P; Snoeyink, V L; Bebee, J; Jim, K K; Beckett, M A; Kriven, W M; Clement, J A

2004-03-01

Iron release from corroded iron pipes is the principal cause of "colored water" problems in drinking water distribution systems. The corrosion scales present in corroded iron pipes restrict the flow of water, and can also deteriorate the water quality. This research was focused on understanding the effect of dissolved oxygen (DO), a key water quality parameter, on iron release from the old corroded iron pipes. Corrosion scales from 70-year-old galvanized iron pipe were characterized as porous deposits of Fe(III) phases (goethite (alpha-FeOOH), magnetite (Fe(3)O(4)), and maghemite (alpha-Fe(2)O(3))) with a shell-like, dense layer near the top of the scales. High concentrations of readily soluble Fe(II) content was present inside the scales. Iron release from these corroded pipes was investigated for both flow and stagnant water conditions. Our studies confirmed that iron was released to bulk water primarily in the ferrous form. When DO was present in water, higher amounts of iron release was observed during stagnation in comparison to flowing water conditions. Additionally, it was found that increasing the DO concentration in water during stagnation reduced the amount of iron release. Our studies substantiate that increasing the concentration of oxidants in water and maintaining flowing conditions can reduce the amount of iron release from corroded iron pipes. Based on our studies, it is proposed that iron is released from corroded iron pipes by dissolution of corrosion scales, and that the microstructure and composition of corrosion scales are important parameters that can influence the amount of iron released from such systems.

Distribution and chemistry of suspended particles from an active hydrothermal vent site on the Mid-Atlantic Ridge at 26°N

NASA Astrophysics Data System (ADS)

Trocine, Robert P.; Trefry, John H.

1988-04-01

Suspended particles were collected from an area of active hydrothermal venting at the Trans-Atlantic Geotraverse (TAG) Hydrothermal Field on the Mid-Atlantic Ridge and analyzed for Fe, Mn, Cd, Zn, Cu, V, Ni, Cr, Pb, Mg, Ca, Al and Si. Rapid advection of vent-derived precipitates produced a lens with total suspended matter (TSM) loadings of 14-60 μg/l at 200-700 m above the seafloor; TSM concentrations > 60 μg/l were observed only at near-vent sites. The distribution of suspended particles correlated well with increased dissolved Mn concentrations and particulate Fe values near the vent source. Particulate Fe values decreased linearly relative to TSM concentrations as hydrothermal precipitates mixed with background suspended matter. Near-vent precipitates were characterized by up to 35% Fe, 2% Zn, 0.6% Cu and > 100 μg/g Cd. In comparison to Fe, particulate Cd, Zn and Cu values decreased dramatically away from the vent source. This trend supports differential settling and/or dissolution of Cd-, Zn- and Cu-bearing phases. Particulate Mn and Fe values were inversely related with only 50 μg Mn/g in the near-vent particles. At near-vent sites, > 99% of the total Mn was in solution; this fraction decreased to 75-80% at background TSM values. In contrast to Cd, Zn and Cu, particulate V levels show a continuous, linear decrease with particulate Fe values. This trend is explained by adsorption of V on Fe-oxides in the vent plume. Scavenging of Cr, Pb and Mg by hydrothermal precipitates is also suggested by the data. Nickel and Al values were low in near-vent particles at < 100 and < 3 μg/g, respectively. The complementary behavior of dissolved Mn and particulate trace metals provides a useful framework for studying broad aspects of hydrothermal plume processes.

Localized zones of denitrification in a floodplain aquifer in southern Wisconsin, USA

NASA Astrophysics Data System (ADS)

Craig, Laura; Bahr, Jean M.; Roden, Eric E.

2010-12-01

A floodplain aquifer within an agricultural watershed near Madison, Wisconsin (USA), was studied to determine whether denitrification was occurring below the surface organic layer. Groundwater levels and concentrations of O2, Cl-, NO{3/-}, SO{4/2-}, dissolved organic carbon (DOC), and major cations were monitored over a 1-year period along a 230-m transect between an agricultural field and a stream discharge point. Seventeen groundwater samples were analyzed for δ15NNO3 and δ18ONO3 composition. Samples in which NO{3/-} was too low for stable isotope analysis were analyzed for excess dissolved N2. Groundwater NO{3/-} concentrations declined between the agricultural field and the discharge point. Chloride and δ15NNO3/δ18ONO3 data indicated that the drop in NO{3/-} was caused primarily by dilution of shallow NO{3/-}-rich water with deeper, NO{3/-}-depleted groundwater. Two localized zones of denitrification were identified in the upland-wetland transition by their δ15NNO3 and δ18ONO3 signatures, and two in the stream hyporheic zone by the presence of excess dissolved N2. The combined stratigraphic, hydrologic, and geochemical data in these locations correspond to groundwater mixing zones where NO{3/-} is delivered to subsurface layers that support denitrification fueled by dissolved (e.g. DOC or dissolved Fe(II)) and/or solid-phase (e.g. particulate organic carbon, solid-associated Fe(II), or pyrite) electron donors.

Effect of Humic Acid on the Removal of Chromium(VI) and the Production of Solids in Iron Electrocoagulation.

PubMed

Pan, Chao; Troyer, Lyndsay D; Liao, Peng; Catalano, Jeffrey G; Li, Wenlu; Giammar, Daniel E

2017-06-06

Iron-based electrocoagulation can be highly effective for Cr(VI) removal from water supplies. However, the presence of humic acid (HA) inhibited the rate of Cr(VI) removal in electrocoagulation, with the greatest decreases in Cr(VI) removal rate at higher pH. This inhibition was probably due to the formation of Fe(II) complexes with HA that are more rapidly oxidized than uncomplexed Fe(II) by dissolved oxygen, making less Fe(II) available for reduction of Cr(VI). Close association of Fe(III), Cr(III), and HA in the solid products formed during electrocoagulation influenced the fate of both Cr(III) and HA. At pH 8, the solid products were colloids (1-200 nm) with Cr(III) and HA concentrations in the filtered fraction being quite high, while at pH 6 these concentrations were low due to aggregation of small particles. X-ray diffraction and X-ray absorption fine structure spectroscopy indicated that the iron oxides produced were a mixture of lepidocrocite and ferrihydrite, with the proportion of ferrihydrite increasing in the presence of HA. Cr(VI) was completely reduced to Cr(III) in electrocoagulation, and the coordination environment of the Cr(III) in the solids was similar regardless of the humic acid loading, pH, and dissolved oxygen level.

Spatio-Temporal Variability of Dissolved Metals in the Surface Waters of an Agroforestry Catchment with Low Levels of Anthropogenic Activity

NASA Astrophysics Data System (ADS)

Soto-Varela, Fátima; Rodríguez-Blanco, M. Luz; Mercedes Taboada-Castro, M.; Taboada-Castro, M. Teresa

2017-12-01

Evaluation of levels and spatial variations of metals in surface waters within a catchment are critical to understanding the extent of land-use impact on the river system. The aims of this study were to investigate the spatial and temporal variations of five dissolved metals (Al, Fe, Mn, Cu and Zn) in surface waters of a small agroforestry catchment (16 km2) in NW Spain. The land uses include mainly forests (65%) and agriculture (pastures: 26%, cultivation: 4%). Stream water samples were collected at four sampling sites distributed along the main course of the Corbeira stream (Galicia, NW Spain) between the headwaters and the catchment outlet. The headwater point can be considered as pristine environment with natural metal concentrations in waters because of the absence of any agricultural activity and limited accessibility. Metal concentrations were determined by ICP-MS. The results showed that metal concentrations were relatively low (Fe > Al > Mn > Zn > Cu), suggesting little influence from agricultural activities in the area. Mn and Zn did not show significant differences between sampling points along main stream, while for Fe and Cu significant differences were found between the headwaters and all other points. Al tended to decrease from the headwaters to the catchment outlet.

Transformation impacts of dissolved and solid phase Fe(II) on trichloroethylene (TCE) reduction in an iron-reducing bacteria (IRB) mixed column system: a mathematical model.

PubMed

Bae, Yeunook; Kim, Dooil; Cho, Hyun-Hee; Singhal, Naresh; Park, Jae-Woo

2012-12-01

In this research, we conducted trichloroethylene (TCE) reduction in a column filled with iron and iron-reducing bacteria (IRB) and developed a mathematical model to investigate the critical reactions between active species in iron/IRB/contaminant systems. The formation of ferrous iron (Fe(II)) in this system with IRB and zero-valent iron (ZVI, Fe(0)) coated with a ferric iron (Fe(III)) crust significantly affected TCE reduction and IRB respiration in various ways. This study presents a new framework for transformation property and reducing ability of both dissolved (Fe(II)(dissolved)) and solid form ferrous iron (Fe(II)(solid)). Results showed that TCE reduction was strongly depressed by Fe(II)(solid) rather than by other inhibitors (e.g., Fe(III) and lactate), suggesting that Fe(II)(solid) might reduce IRB activation due to attachment to IRB cells. Newly exposed Fe(0) from the released Fe(II)(dissolved) was a strong contributor to TCE reduction compared to Fe(II)(solid). In addition, our research confirmed that less Fe(II)(solid) production strongly supported long-term TCE reduction because it may create an easier TCE approach to Fe(0) or increase IRB growth. Our findings will aid the understanding of the contributions of iron media (e.g., Fe(II)(solid), Fe(II)(dissolved), Fe(III), and Fe(0)) to IRB for decontamination in natural groundwater systems. Copyright © 2012 Elsevier Ltd. All rights reserved.

Behavior of tritium permeation induced by water corrosion of alpha iron around room temperature

DOE Office of Scientific and Technical Information (OSTI.GOV)

Otsuka, T.; Hashizume, K.

2015-03-15

Tritium (T) permeation leakage to surroundings is a great safety concern in fission and fusion reactor systems. T permeation potentially occurs from T contaminated water through cooling tubes or storage tank made of metals which dissolve some T evolved by water corrosion. In order to understand behaviors of hydrogen uptake and permeation in pure α-iron (αFe) during water corrosion around room temperature, hydrogen permeation experiments for an αFe membrane have been conducted by means of tritium tracer techniques. The present study suggests that hydrogen produced by water corrosion of αFe is trapped in product oxide layers to delay hydrogen uptakemore » in αFe for a moment. However, the oxide layers do not work as a sufficient barrier for hydrogen uptake. Some of hydrogen dissolved in αFe normally diffuses and permeates through the bulk in the early stage of permeation. In a later stage, hydrogen permeation could be apparently stopped by the disappearance of concentration difference of tritium. Hydrogen partial pressure at the water/αFe interface could be ranged from 0.7 to 9.5 kPa around room temperature.« less

Diurnal variations in, and influences on, concentrations of particulate and dissolved arsenic and metals in the mildly alkaline Wallkill River, New Jersey, USA

USGS Publications Warehouse

Barringer, J.L.; Wilson, T.P.; Szabo, Z.; Bonin, J.L.; Fischer, J.M.; Smith, N.P.

2008-01-01

Diurnal variations in particulate and dissolved As and metal concentrations were observed in mildly alkaline water from a wetlands site on the Wallkill River in northwestern New Jersey. The site, underlain by glacial sediments over dolomite bedrock, is 10 km downstream from a mined area of the Franklin Marble, host to Zn ores, also As and Mn minerals. In mid-September 2005, maxima and minima in dissolved-oxygen-concentration and pH, typically caused by photosynthesis and respiration, occurred at 2000 and 0800 hours. Concentrations of dissolved As (1.52-1.95 ??g/L) peaked at dusk (2000 hours), whereas dissolved Mn and Zn concentrations (76.5-96.9 and 8.55-12.8 ??g/L, respectively) were lowest at dusk and peaked at 1000 hours. These opposing cycles probably reflect sorption and desorption of As (an anion), and Mn and Zn (cations) as pH varied throughout the 24-h period. Doubly-peaked cycles of B, Cl, SO4, and nutrients also were observed; these may result from upstream discharges of septic-system effluent. Both recoverable amd particulate Al, Fe, Mn, and Zn concentrations peaked between 0200 and 0600 hours. The particulate metals cycle, with perturbations at 0400 hours, may be influenced by biological activity. ?? 2007 Springer-Verlag.

Seasonal and spatial variation in soil chemistry and anaerobic processes in an Arctic ecosystem

NASA Astrophysics Data System (ADS)

Lipson, D.; Mauritz, M.; Bozzolo, F.; Raab, T. K.; Santos, M. J.; Friedman, E. F.; Rosenbaum, M.; Angenent, L.

2009-12-01

Drained thaw lake basins (DTLB) are the dominant landform in the Arctic coastal plain near Barrow, Alaska. Our previous work in a DTLB showed that Fe(III) and humic substances are important electron acceptors in anaerobic respiration, and play a significant role in the C cycle of these organic-rich soils. In the current study, we investigated seasonal and spatial patterns of availability of electron acceptors and labile substrate, redox conditions and microbial activity. Landscapes within DTLB contain complex, fine-scale topography arising from ice wedge polygons, which produce raised and lowered areas. One goal of our study was to determine the effects of microtopographic variation on the potential for Fe(III) reduction and other anaerobic processes. Additionally, the soil in the study site has a complex vertical structure, with an organic peat layer overlying a mineral layer, overlying permafrost. We described variations in soil chemistry across depth profiles into the permafrost. Finally, we installed an integrated electrode/potentiostat system to electrochemically monitor microbial activity in the soil. Topographically low areas differed from high areas in most of the measured variables: low areas had lower oxidation-reduction potential, higher pH and electrical conductivity. Soil pore water from low areas had higher concentrations of Fe(III), Fe(II), dissolved organic C (DOC), and aromaticity (UV absorbance at 260nm, “A260”). Low areas also had higher concentrations of dissolve CO2 and CH4 in soil pore water. Laboratory incubations of soil showed a trend toward higher potentials for Fe(III) reduction in topographically low areas. Clearly, ice wedge-induced microtopography exerts a strong control on microbial processes in this DTLB landscape, with increased anaerobic activity occurring in the wetter, depressed areas. Soil water extracted from 5-15 cm depth had higher concentrations of Fe(III), Fe(II), A260, and DOC compared to soil water sampled from 0-5cm. The soil depth profile showed highest concentrations of acid-extractable Fe in the mineral layer and permafrost, though Fe(III) was highest in the surface layer. Total and soluble C increased with depth, as did the potential for CO2 and CH4 production in anaerobic incubations. Thus, the mineral layer may be a significant source of Fe for oxidation-reduction reactions that occur at shallower depths, though methanogenesis dominates in the mineral layer, while Fe(III) reduction dominates in the organic layer. Most of the ions measured in the soil pore water (Fe(III), DOC, A260) showed the same general seasonal pattern: high concentrations soon after soils thawed, declining over time until mid-August. Concentrations of Fe(II) in soil pore water were fairly stable over time. There was a significant positive relationship between A260 and Fe(III) concentrations, possibly indicating the presence of microbially-produced aromatic chelating molecules. Potentiostat measurements confirmed the presence of an electrochemically active microbial community in the soil.

Optimal Soil Eh, pH, and Water Management for Simultaneously Minimizing Arsenic and Cadmium Concentrations in Rice Grains.

PubMed

Honma, Toshimitsu; Ohba, Hirotomo; Kaneko-Kadokura, Ayako; Makino, Tomoyuki; Nakamura, Ken; Katou, Hidetaka

2016-04-19

Arsenic (As) and cadmium (Cd) concentrations in rice grains are a human health concern. We conducted field experiments to investigate optimal conditions of Eh and pH in soil for simultaneously decreasing As and Cd accumulation in rice. Water managements in the experiments, which included continuous flooding and intermittent irrigation with different intervals after midseason drainage, exerted striking effects on the dissolved As and Cd concentrations in soil through changes in Eh, pH, and dissolved Fe(II) concentrations in the soil. Intermittent irrigation with three-day flooding and five-day drainage was found to be effective for simultaneously decreasing the accumulation of As and Cd in grain. The grain As and Cd concentrations were, respectively, linearly related to the average dissolved As and Cd concentrations during the 3 weeks after heading. We propose a new indicator for expressing the degree to which a decrease in the dissolved As or Cd concentration is compromised by the increase in the other. For minimizing the trade-off relationship between As and Cd in rice grains in the field investigated, water management strategies should target the realization of optimal soil Eh of -73 mV and pH of 6.2 during the 3 weeks after heading.

Assessing the utility of dissolved organic matter photoreactivity as a predictor of in situ methylmercury concentration.

PubMed

Klapstein, Sara J; Ziegler, Susan E; Risk, David A; O'Driscoll, Nelson J

2018-06-01

Methylmercury (MeHg) bioaccumulation is a growing concern in ecosystems worldwide. The absorption of solar radiation by dissolved organic matter (DOM) and other photoreactive ligands can convert MeHg into less toxic forms of mercury through photodemethylation. In this study, spectral changes and photoreactivity of DOM were measured to assess the potential to control photoreactions and predict in situ MeHg concentration. Water samples collected from a series of lakes in southwestern Nova Scotia in June, August, and September were exposed to controlled ultraviolet-A (UV-A) radiation for up to 24hr. Dissolved organic matter photoreactivity, measured as the loss of absorbance at 350nm at constant UV-A irradiation, was positively dependent on the initial DOM concentration in lake waters (r 2 =0.94). This relationship was consistent over time with both DOM concentration and photoreactivity increasing from summer into fall across lakes. Lake in situ MeHg concentration was positively correlated with DOM concentration and likely catchment transport in June (r=0.77) but not the other sampling months. Despite a consistent seasonal variation in both DOM and Fe, and their respective correlations with MeHg, no discernable seasonal trend in MeHg was observed. However, a 3-year dataset from the 6 study lakes revealed a positive correlation between DOM concentration and both Fe (r=0.91) and MeHg concentrations (r=0.51) suggesting a more dominant landscape mobility control on MeHg. The DOM-MeHg relationships observed in these lakes highlights the need to examine DOM photoreactivity controls on MeHg transport and availability in natural waters particularly given future climate perturbations. Copyright © 2018. Published by Elsevier B.V.

Modern water/rock reactions in Oman hyperalkaline peridotite aquifers and implications for microbial habitability

NASA Astrophysics Data System (ADS)

Miller, Hannah M.; Matter, Jürg M.; Kelemen, Peter; Ellison, Eric T.; Conrad, Mark E.; Fierer, Noah; Ruchala, Tyler; Tominaga, Masako; Templeton, Alexis S.

2016-04-01

The Samail ophiolite in Oman is undergoing modern hydration and carbonation of peridotite and may host a deep subsurface biosphere. Previous investigations of hyperalkaline fluids in Oman have focused on fluids released at surface seeps, which quickly lose their reducing character and precipitate carbonates upon contact with the O2/CO2-rich atmosphere. In this work, geochemical analysis of rocks and fluids from the subsurface provides new insights into the operative reactions in serpentinizing aquifers. Serpentinite rock and hyperalkaline fluids (pH > 10), which exhibit millimolar concentrations of Ca2+, H2 and CH4, as well as variable sulfate and nitrate, were accessed from wells situated in mantle peridotite near Ibra and studied to investigate their aqueous geochemistry, gas concentrations, isotopic signatures, mineralogy, Fe speciation and microbial community composition. The bulk mineralogy of drill cuttings is dominated by olivine, pyroxene, brucite, serpentine and magnetite. At depth, Fe-bearing brucite is commonly intermixed with serpentine, whereas near the surface, olivine and brucite are lost and increased magnetite and serpentine is detected. Micro-Raman spectroscopy reveals at least two distinct generations of serpentine present in drill cuttings recovered from several depths from two wells. Fe K-edge X-ray absorption near-edge spectroscopy (XANES) analysis of the lizardite shows a strong tetrahedral Fe coordination, suggesting a mixture of both Fe(II) and Fe(III) in the serpentine. Magnetite veins are also closely associated with this second generation serpentine, and 2-10 μm magnetite grains overprint all minerals in the drill cuttings. Thus we propose that the dissolved H2 that accumulates in the subsurface hyperalkaline fluids was evolved through low temperature oxidation and hydration of relict olivine, as well as destabilization of pre-existing brucite present in the partially serpentinized dunites and harzburgites. In particular, we hypothesize that Fe-bearing brucite is currently reacting with dissolved silica in the aquifer fluids to generate late-stage magnetite, additional serpentine and dissolved H2. Dissolved CH4 in the fluids exhibits the most isotopically heavy carbon in CH4 reported in the literature thus far. The CH4 may have formed through abiotic reduction of dissolved CO2 or through biogenic pathways under extreme carbon limitation. The methane isotopic composition may have also been modified by significant methane oxidation. 16S rRNA sequencing of DNA recovered from filtered hyperalkaline well fluids reveals an abundance of Meiothermus, Thermodesulfovibrionaceae (sulfate-reducers) and Clostridia (fermenters). The fluids also contain candidate phyla OP1 and OD1, as well as Methanobacterium (methanogen) and Methylococcus sp. (methanotroph). The composition of these microbial communities suggests that low-temperature hydrogen and methane generation, coupled with the presence of electron acceptors such as nitrate and sulfate, sustains subsurface microbial life within the Oman ophiolite.

Biogeochemical Insights into B-Vitamins in the Coastal Marine Sediments of San Pedro Basin, CA

NASA Astrophysics Data System (ADS)

Monteverde, D.; Berelson, W.; Baronas, J. J.; Sanudo-Wilhelmy, S. A.

2015-12-01

Coastal marine sediments support a high abundance of mircoorganisms which play key roles in the cycling of nutrients, trace metals, and carbon, yet little is known about many of the cofactors essential for their growth, such as the B-vitamins. The suite of B-vitamins (B1, B2, B6, B7, B12) are essential across all domains of life for both primary and secondary metabolism. Therefore, studying sediment concentrations of B-vitamins can provide a biochemical link between microbial processes and sediment geochemistry. Here we present B-vitamin pore water concentrations from suboxic sediment cores collected in September 2014 from San Pedro Basin, a silled, low oxygen, ~900 m deep coastal basin in the California Borderlands. We compare the B-vitamin concentrations (measured via LCMS) to a set of geochemical profiles including dissolved Fe (65-160 μM), dissolved Mn (30-300 nM), TCO2, solid phase organic carbon, and δ13C. Our results show high concentrations (0.8-3nM) of biotin (B7), commonly used for CO2 fixation as a cofactor in carboxylase enzymes. Thiamin (B1) concentrations were elevated (20-700nM), consistent with previous pore water measurements showing sediments could be a source of B1 to the ocean. Cobalamin (B12), a cofactor required for methyl transfers in methanogens, was also detected in pore waters (~4-40pM). The flavins (riboflavin [B2] and flavin mononucleotide[FMN]), molecules utilized in external electron transfer, showed a distinct increase with depth (10-90nM). Interestingly, the flavin profiles showed an inverse trend to dissolved Fe (Fe decreases with depth) providing a potential link to culture experiments which have shown extracellular flavin release to be a common trait in some metal reducers. As some of the first B-vitamin measurements made in marine sediments, these results illustrate the complex interaction between the microbial community and surrounding geochemical environment and provide exciting avenues for future research.

The Distribution of Dissolved Iron in the West Atlantic Ocean

PubMed Central

Rijkenberg, Micha J. A.; Middag, Rob; Laan, Patrick; Gerringa, Loes J. A.; van Aken, Hendrik M.; Schoemann, Véronique; de Jong, Jeroen T. M.; de Baar, Hein J. W.

2014-01-01

Iron (Fe) is an essential trace element for marine life. Extremely low Fe concentrations limit primary production and nitrogen fixation in large parts of the oceans and consequently influence ocean ecosystem functioning. The importance of Fe for ocean ecosystems makes Fe one of the core chemical trace elements in the international GEOTRACES program. Despite the recognized importance of Fe, our present knowledge of its supply and biogeochemical cycle has been limited by mostly fragmentary datasets. Here, we present highly accurate dissolved Fe (DFe) values measured at an unprecedented high intensity (1407 samples) along the longest full ocean depth transect (17500 kilometers) covering the entire western Atlantic Ocean. DFe measurements along this transect unveiled details about the supply and cycling of Fe. External sources of Fe identified included off-shelf and river supply, hydrothermal vents and aeolian dust. Nevertheless, vertical processes such as the recycling of Fe resulting from the remineralization of sinking organic matter and the removal of Fe by scavenging still dominated the distribution of DFe. In the northern West Atlantic Ocean, Fe recycling and lateral transport from the eastern tropical North Atlantic Oxygen Minimum Zone (OMZ) dominated the DFe-distribution. Finally, our measurements showed that the North Atlantic Deep Water (NADW), the major driver of the so-called ocean conveyor belt, contains excess DFe relative to phosphate after full biological utilization and is therefore an important source of Fe for biological production in the global ocean. PMID:24978190

Phosphorus mitigation during springtime runoff by amendments applied to grassed soil.

PubMed

Uusi-Kämppä, J; Turtola, E; Närvänen, A; Jauhiainen, L; Uusitalo, R

2012-01-01

Permanent grass vegetation on sloping soils is an option to protect fields from erosion, but decaying grass may liberate considerable amounts of dissolved reactive P (DRP) in springtime runoff. We studied the effects of freezing and thawing of grassed soil on surface runoff P concentrations by indoor rainfall simulations and tested whether the peak P concentrations could be reduced by amending the soil with P-binding materials containing Ca or Fe. Forty grass-vegetated soil blocks (surface area 0.045 m, depth 0.07 m) were retrieved from two permanent buffer zones on a clay and loam soil in southwest Finland. Four replicates were amended with either: (i) gypsum from phosphoric acid processing (CaSO × 2HO, 6 t ha), (ii) chalk powder (CaCO, 3.3 t ha), (iii) Fe-gypsum (6 t ha) from TiO processing, or (iv) granulated ferric sulfate (Fe[SO], 0.7 t ha), with four replicates serving as untreated controls. Rainfall (3.3 h × 5 mm h) was applied on presaturated samples set at a slope of 5% and the surface runoff was analyzed for DRP, total dissolved P (TDP), total P (TP), and suspended solids. Rainfall simulation was repeated twice after the samples were frozen. Freezing and thawing of the samples increased the surface runoff DRP concentration of the control treatment from 0.19 to 0.46 mg L, up to 2.6-3.7 mg L, with DRP being the main P form in surface runoff. Compared with the controls, surface runoff from soils amended with Fe compounds had 57 to 80% and 47 to 72% lower concentrations of DRP and TP, respectively, but the gypsum and chalk powder did not affect the P concentrations. Thus, amendments containing Fe might be an option to improve DRP retention in, e.g., buffer zones. Copyright © by the American Society of Agronomy, Crop Science Society of America, and Soil Science Society of America, Inc.

Diel variations in stream chemistry and isotopic composition of dissolved inorganic carbon, upper Clark Fork River, Montana, USA

USGS Publications Warehouse

Parker, Stephen R.; Gammons, Christopher H.; Poulson, Simon R.; DeGrandpre, Michael D.

2007-01-01

Many rivers undergo diel (24-h) concentration fluctuations of pH, dissolved gases, trace metals, nutrients, and other chemical species. A study conducted in 1994 documented such behavior in the upper Clark Fork River, Montana, a stream whose headwaters have been severely impacted by historic metal mining, milling, and smelting. The purpose of the present investigation was to expand on these earlier findings by conducting simultaneous diel samplings at two sites on the upper Clark Fork River separated by 2.5 h of stream travel time. By monitoring two stations, it was possible to more closely examine the processes that control temporal and spatial gradients in stream chemistry. Another objective was to examine diel changes in the δ13C composition of dissolved inorganic C (DIC) and their relationship to biological activity in the stream. The most important findings of this study include: (1) concentrations of dissolved and particulate heavy metals increased during the night and decreased during the day, in agreement with previous work; (2) these changes were positively correlated to diel changes in pH, dissolved O2, and water temperature; (3) dissolved concentrations increased during the night at the lower site, but showed the opposite behavior at the upper site; and (4) diel changes in δ13C-DIC were noted at both sites, although the timing and magnitudes of the cycles differed. Hypotheses to explain the first two observations include: cyclic co-precipitation of divalent metals with carbonate minerals; pH- and temperature-dependent sorption of metal cations onto the streambed and suspended particles; or photosynthetically enhanced oxidation and removal of Fe and Mn oxides at biofilm surfaces during the daytime. The latter model explains the majority of the field observations, including night-time increases in particulate forms of Fe and other elements.

Dissolved organic matter degradation by sunlight coagulates organo-mineral colloids and produces low-molecular weight fraction of metals in boreal humic waters

NASA Astrophysics Data System (ADS)

Oleinikova, Olga V.; Drozdova, Olga Yu.; Lapitskiy, Sergey A.; Demin, Vladimir V.; Bychkov, Andrey Yu.; Pokrovsky, Oleg S.

2017-08-01

Photochemical degradation of dissolved organic matter (DOM) is recognized as the major driver of CO2 emission to the atmosphere from the inland waters of high latitudes. In contrast to numerous studies of photo-induced DOM transformation, the behavior of trace element (TE) during photodegradation of boreal DOM remains virtually unknown. Towards a better understanding of concentration, size fractionation and speciation change of DOM and TE in boreal waters subjected to solar radiation, we conducted on-site photo-degradation experiments in stream and bog water collected from a pristine zone of the Northern Karelia (Russian subarctic). The removal of Fe and Al occurred only in the bog water (90% and 50% respectively, over 5 days of reaction), whereas no detectable decrease of dissolved (<0.22 μm) Al and Fe concentration was observed in the boreal stream. A number of low-soluble TE linked to Fe-rich organo-mineral colloids followed the behavior of Fe during bog water exposure to sunlight: Al, P, Ti, V, Cr, As, Y, Zr, REEs, Hf, Th, Pb and U. The second group of elements (Li, B, Mg, Ca, Sr, Ba, Na, K, Rb, Si, Mn, Ni, Cu, Co, Cd, Sb) was indifferent to photodegradation of DOM and exhibited a non-systematic variation (±10-15% from the control) of <0.22 μm fraction in the course of sunlight exposure. The bog water insolation yielded a factor of 3 ± 1 increase of low molecular weight (LMW < 1 kDa) fraction of organic carbon, Al, Fe, U, Mg, Ca, Mn, Co, Ni, Sr, Cd and Ba after 200 h of sunlight exposure compared to the dark control. The LMW< 1 kDa fraction was preferentially enriched in Fe, Al, Ca, Mg and other divalent metals relative to Corg. The climate warming leading to water temperature rise in the boreal zone will intensify the Fe and Al hydroxide coagulation while increasing the production of LMW organic ligands and free metals and metal - organic complexes.

In situ iron activated persulfate oxidative fluid sparging treatment of TCE contamination--a proof of concept study.

PubMed

Liang, Chenju; Lee, I-Ling

2008-09-10

In situ chemical oxidation (ISCO) is considered a reliable technology to treat groundwater contaminated with high concentrations of organic contaminants. An ISCO oxidant, persulfate anion (S(2)O(8)(2-)) can be activated by ferrous ion (Fe(2+)) to generate sulfate radicals (E(o)=2.6 V), which are capable of destroying trichloroethylene (TCE). The property of polarity inhibits S(2)O(8)(2-) or sulfate radical (SO(4)(-)) from effectively oxidizing separate phase TCE, a dense non-aqueous phase liquid (DNAPL). Thus the oxidation primarily takes place in the aqueous phase where TCE is dissolved. A bench column study was conducted to demonstrate a conceptual remediation method by flushing either S(2)O(8)(2-) or Fe(2+) through a soil column, where the TCE DNAPL was present, and passing the dissolved mixture through either a Fe(2+) or S(2)O(8)(2-) fluid sparging curtain. Also, the effect of a solubility enhancing chemical, hydroxypropyl-beta-cyclodextrin (HPCD), was tested to evaluate its ability to increase the aqueous TCE concentration. Both flushing arrangements may result in similar TCE degradation efficiencies of 35% to 42% estimated by the ratio of TCE degraded/(TCE degraded+TCE remained in effluent) and degradation byproduct chloride generation rates of 4.9 to 7.6 mg Cl(-) per soil column pore volume. The addition of HPCD did greatly increase the aqueous TCE concentration. However, the TCE degradation efficiency decreased because the TCE degradation was a lower percentage of the relatively greater amount of dissolved TCE by HPCD. This conceptual treatment may serve as a reference for potential on-site application.

Reactive iron and manganese in estuarine sediments of the Baltic Sea: Impacts of flocculation and redox shuttling

NASA Astrophysics Data System (ADS)

Jilbert, Tom; Tiihonen, Rosa; Myllykangas, Jukka-Pekka; Asmala, Eero; Hietanen, Susanna

2016-04-01

Iron (Fe) and manganese (Mn) play important roles in sedimentary carbon cycling in both freshwater and marine systems. Dissimilatory reduction of Fe and Mn oxides is known to be a major pathway of suboxic organic matter remineralization in surface sediments, while recent studies have shown that Fe and Mn oxides may be involved in the anaerobic oxidation of methane deeper in the sediment column (e.g., Egger et al., 2015). Estuaries are transitional environments, characterized by gradients of salinity and redox conditions which impact on the mobility of Fe and Mn. In turn, the distribution of Fe and Mn in estuarine sediments, and the role of the two metals in carbon cycling, is expected to be spatially heterogeneous. However, few studies have attempted to describe the sedimentary distribution of Fe and Mn in the context of processes occurring in the estuarine water column. In particular, salinity-driven flocculation and redox shuttling are two key processes whose relative impacts on sedimentary Fe and Mn have not been clearly demonstrated. In this study we investigated the coupled water column and sedimentary cycling of Fe and Mn along a 60km non-tidal estuarine transect in the Gulf of Finland, Baltic Sea. We show that riverine Fe entering the estuary as colloidal oxides associated with dissolved organic matter (DOM) is quickly flocculated and sedimented within 5 km of the river mouth, despite the shallow lateral salinity gradient. Sediments within this range are enriched in Fe (up to twice the regional average), principally in the form of crystalline Fe oxides as determined by sequential extractions. The high crystallinity implies relative maturity of the oxide mineralogy, likely due to sustained oxic conditions and long residence time in the river catchment. Despite the reducing conditions below the sediment-water interface, Fe is largely retained in the sediments close to the river mouth. In contrast, sedimentary Mn concentrations are highest in a deep silled basin more than 10km downstream. Throughout the estuary, Mn oxides are reductively dissolved shallower in the sediment column than Fe oxides, resulting in strong effluxes of dissolved Mn from the sediments. Subsequent oxidation of bottom water dissolved Mn to particulate oxides and lateral transport ("redox shuttling") account for the sedimentary Mn enrichments in the deep silled basin. Porewater data suggest that the heterogeneity of Fe and Mn availability in the estuarine sediments may influence the relative importance of the two metals for anaerobic oxidation of methane. Egger, M. et al., Environmental Science and Technology 49(1), 277-283, 2015.

Chemical characteristics of dissolved organic matter (DOM) in relation to heavy metal concentrations in soil water from boreal peatlands after clear-cut harvesting

NASA Astrophysics Data System (ADS)

Kiikkilä, O.; Nieminen, T.; Starr, M.; Ukonmaanaho, L.

2012-04-01

Boreal peatlands form an important terrestrial carbon reserve and are a major source of dissolved organic matter (DOM) to surface waters, particularly when disturbed through forestry practices such as draining or timber harvesting. Heavy metals show a strong affinity to organic matter and so, along with DOM, heavy metals can be mobilized and transported from the soil to surface waters and sediments where they may become toxic to aquatic organisms and pass up the food chain. The complexation of heavy metals with DOM can be expected to be related and determined by the chemical characteristics of DOM and oxidation/reducing conditions in the peat. We extracted interstitial water from peat samples and determined the concentrations of dissolved organic carbon (DOC), dissolved organic nitrogen (DON) and Al, Cu, Zn and Fe in various fractions of DOM isolated by adsorption properties (XAD-8 fractionation) and molecular-weight (ultrafiltration). The peat samples were taken from 0-30 and 30-50 cm depth in drained peatland catchments two years after whole-tree or stem-only clear-cut harvesting (Scots pine or Norway spruce) had been carried out. The samples from the upper layer had been subject to alternating saturation/aeration conditions while the deeper layer had been continuously under the water table. The fractionation of DOC and DON according to both adsorption properties and molecular-weight fractions clearly differed between the upper and lower peat layers. While the hydrophobic acid fraction contained proportionally more DOC and DON than the hydrophilic acid fraction in the upper peat layer the results were vice versa in the lower peat layer. High-molecular-weight compounds (> 100 kDa) were proportionally more abundant in the upper and low-molecular-weight compounds (< 1 kDa) in the lower peat layer. These differences are assumed to reflect differences in the aerobic/ anaerobic conditions and degree of decomposition between the two layers. The concentrations of Zn, Al, Fe and DON correlated positively with DOC concentrations whereas the concentration Cu did not correlate with DOC concentrations. Heavy metal concentrations in different molecular-weight fractions indicated that Al, Cu, Zn and Fe were mostly associated with high-molecular-weight compounds and only a small fraction existed as free metal ions in solution. There were no clear differences in the chemical characteristics of DOC or DON or heavy metal concentrations between the two harvesting treatments.

Major ions, nutrients, and trace elements in the Mississippi River near Thebes, Illinois, July through September 1993

USGS Publications Warehouse

Taylor, Howard E.; Antweiler, Ronald C.; Brinton, Terry I.; Roth, David A.; Moody, John A.

1994-01-01

Extensive flooding in the upper Mississippi River Basin during summer 1993 had a significant effect on the water quality of the Mississippi River. To evaluate the change in temporal distribution and transport of dissolved constituents in the Mississippi River, six water samples were collected by a discharge-weighted method from July through September 1993 near Thebes, Illinois. Sampling at this location provided water-quality information from the upper Mississippi, the Missouri, and the Illinois River Basins. Dissolved major constituents that were analyzed in each of the samples included bicarbonate, calcium (Ca), carbonate (C03), chloride (Cl), dissolved organic carbon, magnesium (Mg), potassium (K), silica NOD, sodium (Na), and sulfate (S04). Dissolved nutrients included ammonium ion (NH4), nitrate (N03), nitrite (N02), and orthophosphate (P04) . Dissolved trace elements included aluminum (Al), arsenic (As), barium (Ba), boron (B), beryllium (Be), bromide (Br), cadmium (Cd), chromium (Cr), cobalt, (Co), copper (Cu), fluoride (F), iron (Fe), lead, lithium (Li), manganese (Mn), mercury (Hg), molybdenum (Mo), nickel (Ni), strontium (Sr), thallium, uranium (U), vanadium (V), and zinc (Zn). Other physical properties of water that were measured included specific conductance, pH and suspended-sediment concentration (particle size, less than 63 micrometers). Results of this study indicated that large quantities of dissolved constituents were transported through the river system. Generally, pH, alkalinity, and specific conductance and the concentrations of B, Br, Ca, Cl, Cr, K, Li, Mg, Mo, Na, S04, Sr, U, and V increased as water discharge decreased, while concentrations of F, Hg, and suspended sediment sharply decreased as water discharge decreased after the crest of the flood. Concentrations of other constituents, such as Al, As, Ba, Be, Co, Cu, Ni, N03, N02, NH4, P04, and Si02, varied with time as discharge decreased after the crest of the flood. For most constituents, the load transported during floods generally is much greater than that transported during low-flow conditions. How ever, for Cd, Cr, Fe, Mn, V, and Zn, loads increased substantially as water discharge decreased after the crest of the flood.

A record of deep-ocean dissolved O2 from the oxidation state of iron in submarine basalts.

PubMed

Stolper, Daniel A; Keller, C Brenhin

2018-01-18

The oxygenation of the deep ocean in the geological past has been associated with a rise in the partial pressure of atmospheric molecular oxygen (O 2 ) to near-present levels and the emergence of modern marine biogeochemical cycles. It has also been linked to the origination and diversification of early animals. It is generally thought that the deep ocean was largely anoxic from about 2,500 to 800 million years ago, with estimates of the occurrence of deep-ocean oxygenation and the linked increase in the partial pressure of atmospheric oxygen to levels sufficient for this oxygenation ranging from about 800 to 400 million years ago. Deep-ocean dissolved oxygen concentrations over this interval are typically estimated using geochemical signatures preserved in ancient continental shelf or slope sediments, which only indirectly reflect the geochemical state of the deep ocean. Here we present a record that more directly reflects deep-ocean oxygen concentrations, based on the ratio of Fe 3+ to total Fe in hydrothermally altered basalts formed in ocean basins. Our data allow for quantitative estimates of deep-ocean dissolved oxygen concentrations from 3.5 billion years ago to 14 million years ago and suggest that deep-ocean oxygenation occurred in the Phanerozoic (541 million years ago to the present) and potentially not until the late Palaeozoic (less than 420 million years ago).

A record of deep-ocean dissolved O2 from the oxidation state of iron in submarine basalts

NASA Astrophysics Data System (ADS)

Stolper, Daniel A.; Keller, C. Brenhin

2018-01-01

The oxygenation of the deep ocean in the geological past has been associated with a rise in the partial pressure of atmospheric molecular oxygen (O2) to near-present levels and the emergence of modern marine biogeochemical cycles. It has also been linked to the origination and diversification of early animals. It is generally thought that the deep ocean was largely anoxic from about 2,500 to 800 million years ago, with estimates of the occurrence of deep-ocean oxygenation and the linked increase in the partial pressure of atmospheric oxygen to levels sufficient for this oxygenation ranging from about 800 to 400 million years ago. Deep-ocean dissolved oxygen concentrations over this interval are typically estimated using geochemical signatures preserved in ancient continental shelf or slope sediments, which only indirectly reflect the geochemical state of the deep ocean. Here we present a record that more directly reflects deep-ocean oxygen concentrations, based on the ratio of Fe3+ to total Fe in hydrothermally altered basalts formed in ocean basins. Our data allow for quantitative estimates of deep-ocean dissolved oxygen concentrations from 3.5 billion years ago to 14 million years ago and suggest that deep-ocean oxygenation occurred in the Phanerozoic (541 million years ago to the present) and potentially not until the late Palaeozoic (less than 420 million years ago).

Coupled S and Sr isotope evidences for elevated arsenic concentrations in groundwater from the world's largest antimony mine, Central China

NASA Astrophysics Data System (ADS)

Wen, Bing; Zhou, Aiguo; Zhou, Jianwei; Liu, Cunfu; Huang, Yuliu; Li, Ligang

2018-02-01

The Xikuangshan(XKS) mine, the world's largest antimony mine, was chosen for a detailed arsenic hydrogeochemical study because of the elevated arsenic in bedrock aquifers used by local residents. Hydrochemical data, δ34S values of dissolved SO42- and 87Sr/86Sr ratios have been analyzed to identify the predominant geochemical processes that control the arsenic mobilization within the aquifers. Groundwater samples can be divided into three major types: low arsenic groundwater (0-50 μg/L), high arsenic groundwater (50-1000 μg/L) and anomalous high arsenic groundwater (>1000 μg/L). Arsenic occurs under oxidizing conditions at the XKS Sb mine as the HAsO42- anion. The Ca/Na ratio correlates significantly with HCO3-/Na and Sr/Na ratios, indicating that carbonate dissolution and silicate weathering are the dominant processes controlling groundwater hydrochemistry. The δ34S values of the groundwater indicate that dissolved SO42- in groundwater is mainly sourced from the oxidation of sulfide minerals, and elevated As concentrations in groundwater are influenced by the mixing of mine water and surface water. Furthermore, the δ34S values are not correlated with dissolved As concentrations and Fe concentrations, suggesting that the reduction dissolution of Fe(III) hydroxides is not the dominant process controlling As mobilization. The 87Sr/86Sr ratios imply that elevated As concentrations in groundwater are primarily derived from the interaction with the stibnite and silicified limestone. More specifically, the excess-Na ion, the feature of Ca/Na ratio, and the spatial association of elevated As concentrations in groundwater collectively suggest that high and anomalous high arsenic groundwater are associated with smelting slags and, in particular, the arsenic alkali residue. In general, the hydrochemistry analysis, especially the S and Sr isotope evidences elucidate that elevated As concentrations and As mobilization are influenced by several geochemical processes, including: (1) bedrock weathering; (2) oxidation of arsenopyrite and the dominant sulfides in the ores; (3) mixing of mine drainage and surface water; (4) leaching of the arsenic alkali residue; and (5) sorption-desorption from Fe/Mn oxides/hydroxides.

Increased concentrations of potassium in heartwood of trees in response to groundwater contamination

NASA Astrophysics Data System (ADS)

Vroblesky, Don A.; Yanosky, Thomas M.; Siegel, Frederic R.

1992-03-01

The wood of tuliptrees ( Liriodendron tulipifera L.) growing above groundwater contamination from a hazardous-waste landfill in Maryland contained elevated concentrations of potassium (K). The groundwater contamination also contained elevated concentrations of dissolved K, as well as arsenic (As), cadmium (Cd), chloride (Cl), iron (Fe), manganese (Mn), zinc (Zn), and organic solvents. The dissolved K is derived from disposed smoke munitions. The excess K in the tuliptrees is concentrated in the heartwood, the part of the xylem most depleted in K in trees growing outside of the contamination. These data show that the uptake and translocation of K by tuliptrees can be strongly influenced by the availability of K in groundwater contamination and suggest the utility of this species as an areal indicator of groundwater contamination.

Pathways and supply of dissolved iron in the Amundsen Sea (Antarctica)

NASA Astrophysics Data System (ADS)

St-Laurent, P.; Yager, P. L.; Sherrell, R. M.; Stammerjohn, S. E.; Dinniman, M. S.

2017-09-01

Numerous coastal polynyas fringe the Antarctic continent and strongly influence the productivity of Antarctic shelf systems. Of the 46 Antarctic coastal polynyas documented in a recent study, the Amundsen Sea Polynya (ASP) stands out as having the highest net primary production per unit area. Incubation experiments suggest that this productivity is partly controlled by the availability of dissolved iron (dFe). As a first step toward understanding the iron supply of the ASP, we introduce four plausible sources of dFe and simulate their steady spatial distribution using conservative numerical tracers. The modeled distributions replicate important features from observations including dFe maxima at the bottom of deep troughs and enhanced concentrations near the ice shelf fronts. A perturbation experiment with an idealized drawdown mimicking summertime biological uptake and subsequent resupply suggests that glacial meltwater and sediment-derived dFe are the main contributors to the prebloom dFe inventory in the top 100 m of the ASP. The sediment-derived dFe depends strongly on the buoyancy-driven overturning circulation associated with the melting ice shelves (the "meltwater pump") to add dFe to the upper 300 m of the water column. The results support the view that ice shelf melting plays an important direct and indirect role in the dFe supply and delivery to polynyas such as the ASP.

Determination of chemical-constituent loads during base-flow and storm-runoff conditions near historical mines in Prospect Gulch, upper Animas River watershed, southwestern Colorado

USGS Publications Warehouse

Wirt, Laurie; Leib, K.J.; Bove, D.J.; Mast, M.A.; Evans, J.B.; Meeker, G.P.

1999-01-01

Prospect Gulch is a major source of iron, aluminum, zinc, and other metals to Cement Creek. Information is needed to prioritize remediation and develop strategies for cleanup of historical abandoned mine sites in Prospect Gulch. Chemical-constituent loads were determined in Prospect Gulch, a high-elevation alpine stream in southwestern Colorado that is affected by natural acid drainage from weathering of hydro-thermally altered igneous rock and acidic metal-laden discharge from historical abandoned mines. The objective of the study was to identify metal sources to Prospect Gulch. A tracer solution was injected into Prospect Gulch during water-quality sampling so that loading of geochemical constituents could be calculated throughout the study reach. A thunderstorm occurred during the tracer study, hence, metal loads were measured for storm-runoff as well as for base flow. Data from different parts of the study reach represents different flow conditions. The beginning of the reach represents background conditions during base flow immediately upstream from the Lark and Henrietta mines (samples PG5 to PG45). Other samples were collected during storm runoff conditions (PG100 to PG291); during the first flush of metal runoff following the onset of rainfall (PG303 to PG504), and samples PG542 to PG700 were collected during low-flow conditions. During base-flow conditions, the percentage increase in loads for major constituents and trace metals was more than an order of magnitude greater than the corresponding 36 % increase in stream discharge. Within the study reach, the highest percentage increases for dissolved loads were 740 % for iron (Fe), 465 % for aluminum (Al), 500 % for lead (Pb), 380 % for copper (Cu), 100 % for sulfate (SO4), and 50 % for zinc (Zn). Downstream loads near the mouth of Prospect Gulch often greatly exceeded the loads generated within the study reach but varied by metal species. For example, the study reach accounts for about 6 % of the dissolved-Fe load, 13 % of the dissolved-Al load, and 18 % of the dissolved-Zn load; but probably contributes virtually all of the dissolved Cu and Pb. The greatest downstream gains in dissolved trace-metal loads occurred near waste-rock dumps for the historical mines. The major sources of trace metals to the study reach were related to mining. The major source of trace metals in the reach near the mouth is unknown, however is probably related to weathering of highly altered igneous rocks, although an unknown component of trace metals could be derived from mining sources The late-summer storm dramatically increased the loads of most dissolved and total constituents. The effects of the storm were divided into two distinct periods; (1) a first flush of higher metal concentrations that occurred soon after rainfall began and (2) the peak discharge of the storm runoff. The first flush contained the highest loads of dissolved Fe, total and dissolved Zn, Cu, and Cd. The larger concentrations of Fe and sulfate in the first flush were likely derived from iron hydroxide minerals such as jarosite and schwertmanite, which are common on mine dumps in the Prospect Gulch drainage basin. Peak storm runoff contained the highest measured loads of total Fe, and of total and dissolved calcium, magnesium, silica and Al, which were probably derived from weathering of igneous rocks and clay minerals in the drainage basin.

Ferrate(VI) enhanced photocatalytic oxidation of pollutants in aqueous TiO2 suspensions.

PubMed

Sharma, Virender K; Graham, Nigel J D; Li, Xiang-Zhong; Yuan, Bao-Ling

2010-02-01

Photocatalytic oxidation using UV irradiation of TiO(2) has been studied extensively and has many potential industrial applications, including the degradation of recalcitrant contaminants in water and wastewater treatment. A limiting factor in the oxidation process is the recombination of conduction band electrons (e(-)(cb)) with electron holes (h(vb)(+)) on the irradiated TiO(2) surface; thus, in aqueous conditions, the presence of an effective electron scavenger will be beneficial to the efficiency of the oxidation process. Ferrate (FeO(4)(2-)) has received much recent attention as a water treatment chemical since it behaves simultaneously as an oxidant and coagulant. The combination of ferrate [Fe(VI)] with UV/TiO(2) photocatalysis offers an oxidation synergism arising from the Fe(VI) scavenging of e(-)(cb) and the corresponding beneficial formation of Fe(V) from the Fe(VI) reduction. This paper reviews recent studies concerning the photocatalytic oxidation of problematic pollutants with and without ferrate. The paper reviews the published results of laboratory experiments designed to follow the photocatalytic degradation of selected contaminants of environmental significance and the influence of the experimental conditions (e.g. pH, reactant concentrations and dissolved oxygen). The specific compounds are as follows: ammonia, cyanate, formic acid, bisphenol-A, dibutyl- and dimethyl-phthalate and microcystin-LR. The principal focus in these studies has been on the rates of reaction rather than on reaction pathways and products. The presence of UV/TiO(2) accelerates the chemical reduction of ferrate, and the reduction rate decreases with pH owing to deprotonation of ferrate ion. For all the selected contaminant substances, the photocatalytic oxidation rate was greater in the presence of ferrate, and this was believed to be synergistic rather than additive. The presence of dissolved oxygen in solution reduced the degradation rate of dimethyl phthalate in the ferrate/photocatalysis system. In the study of microcystin-LR, it was evident that an optimal ferrate concentration exists, whereby higher Fe(VI) concentrations above the optimum leads to a reduction in microcystin-LR degradation. In addition, the rate of microcystin-LR degradation was found to be strongly dependent on pH and was greatest at pH 6. The initial rate of photocatalytic reduction under different conditions was analysed using a Langmuirian form. Decrease in rates in the presence of dissolved oxygen may be due to competition between oxygen and ferrate as electron scavengers and to non-productive radical species interactions. The reaction between ferrate(VI) and microcystins-LR in the pH range of 6.0-10.0 is most likely controlled by the protonated Fe(VI) species, HFeO(4)(-). The photocatalytic oxidation of selected, recalcitrant contaminants was found to be significantly greater in the presence of ferrate, arising from the role of ferrate in inhibiting the h(vb)(+)-e(-)(cb) pair recombination on TiO(2) surfaces and the corresponding generation of highly oxidative Fe(V) species. The performance of the ferrate/photocatalysis system is strongly influenced by the reaction conditions, particularly the pH and dissolved oxygen concentration, arising from the complex nature of the interactions between the catalyst and the solution. Overall, the treatment performance of the Fe(VI)-TiO(2)-UV system is generally superior to alternative chemical oxidation methods. The formation of intermediate Fe(V) species in the photocatalytic reduction of ferrate(VI) requires confirmation, and a method involving electron paramagnetic resonance spectroscopy could be applied for this. The reactivity of Fe(V) with the selected contaminants is required in order to better understand the role of ferrate in the Fe(VI)-TiO(2)-UV oxidation system. To increase the practical utility of the system, it is recommended that future studies involving the photocatalytic oxidation of pollutants in the presence of ferrate(VI) should focus on developing modified TiO(2) surfaces that are photocatalytic under visible light conditions.

Diel Sampling of Groundwater and Surface Water for Trace Elements and Select Water-Quality Constituents at a Former Zinc Smelter Site near Hegeler, Illinois, August 1-3, 2007

USGS Publications Warehouse

Kay, Robert T.; Groschen, George E.; Dupre, David H.; Drexler, Timothy D.; Thingvold, Karen L.; Rosenfeld, Heather J.

2009-01-01

Surface water can exhibit substantial diel variations in the concentration of a number of constituents. Sampling regimens that do not characterize diel variations in water quality can result in an inaccurate understanding of site conditions and of the threat posed by the site to human health and the environment. Surface- and groundwater affected by acid drainage were sampled every 60 to 90 minutes over a 48-hour period at a former zinc smelter known as the Hegeler Zinc Superfund Site, in Hegeler, Ill. Groundwater-quality data from a well at the site indicate stable, low pH, weakly oxidizing geochemical conditions in the aquifer. With the exceptions of temperature and pH, no constituents exhibited diel variations in groundwater. Variations in temperature and pH likely were not representative of conditions in the aquifer. Surface water was sampled at a site on Grape Creek. Diel variations were observed in temperature, dissolved oxygen, pH, and specific conductance, and in the concentrations of nitrite, barium, iron, lead, vanadium, and possibly uranium. Concentrations during the diel cycles varied by about an order of magnitude for nitrite and varied by about a factor of two for barium, iron, lead, vanadium, and uranium. Temperature, dissolved oxygen, specific conductance, nitrite, barium, lead, and uranium generally reached maximum values during the afternoon and minimum values during the night. Iron, vanadium, and pH generally reached minimum values during the afternoon and maximum values during the night. These variations would need to be accounted for during sampling of surface-water quality in similar hydrologic settings. The temperature variations in surface water were affected by variations in air temperature. Concentrations of dissolved oxygen were affected by variations in the intensity of photosynthetic activity and respiration. Nitrite likely was formed by the oxidation of ammonium by dissolved oxygen and degraded by its anaerobic oxidation by ammonium or as part of the decomposition of organic matter. Variations in pH were affected by the photoreduction of Fe3+ to Fe2+ and the precipitation of iron oxyhydroxides. Diel variations in concentrations of iron and vanadium were likely caused by variations in the dissolution and precipitation of iron oxyhydroxides, oxyhydroxysulfates, and hydrous sulfates, which may have been affected by in the intensity of insolation, iron photoreduction, and the concentration of dissolved oxygen. The concentrations of lead, uranium, and perhaps barium in Grape Creek may have been affected by competition for sorption sites on iron oxyhydroxides. Competition for sorption sites was likely affected by variations in pH and the concentration of Fe2+. Constituent concentrations likely also were affected by precipitation and dissolution of minerals that are sensitive to changes in pH, temperature, oxidation-reduction conditions, and biologic activity. The chemical and biologic processes that resulted in the diel variations observed in Grape Creek occurred within the surface-water column or in the underlying sediments.

Metal discharges by Sinaloa Rivers to the coastal zone of NW Mexico.

PubMed

Frías-Espericueta, M G; Mejía-Cruz, R; Osuna López, I; Muy-Rangel, M D; Rubio-Carrasco, W; Aguilar-Juárez, M; Voltolina, D

2014-02-01

The aim of this work was to survey the discharges of dissolved and particulate Cd, Cu, Fe, Mn, Pb and Zn of the eight main rivers of Sinaloa State to the Mexican coastal environment. Zn was the most abundant dissolved metal and Fe was the most abundant particulate (8.02-16.90 and 51.8-1,140.3 μg/L, respectively). Only particulate Mn had significantly (p = 0.028) higher values in summer-fall (rainy season), whereas the significantly (p = 0.036) higher values of dissolved Zn were observed in winter and spring. The highest annual total discharges to Sinaloa coastal waters were those of the rivers San Lorenzo and Piaxtla (>2 × 10(3) m.t.) and the lowest those of rivers Baluarte and El Fuerte (349 and 119 m.t., respectively). Pb concentrations may become of concern, because they are higher than the value recommended for the welfare of aquatic communities of natural waters.

Key sources and distribution patterns of particulate material in the South Atlantic: data from the UK GEOTRACES A10 cruise

NASA Astrophysics Data System (ADS)

Milne, A.; Palmer, M.; Lohan, M. C.

2016-02-01

Particles play a fundamental role in the biogeochemical cycling of both major- and micro-nutrients in marine systems, including trace elements and isotopes. However, knowledge of particulate distributions, and their potential to regulate dissolved elemental concentrations, remains limited and poorly understood. The paradox is, that the oceanic inventory of trace metals is dominated by particulate inputs (e.g. aerosol deposition, shelf sediment resuspension). Moreover the labile fraction of particulate trace elements could be an important regulator of dissolved concentrations. Here we present particulate data from the UK GEOTRACES South Atlantic transect (GA10) from South Africa to Uruguay. Data from a range of elements (e.g. Fe, Al, Mn) revealed a greater input of particulate metals from the Argentine shelf (up to 290 nM of pFe) in comparison to the South African shelf (< 40 nM of pFe). Overall, higher concentrations of all metals were observed in the bottom waters of the Argentine basin and penetrated deeper up the water column (up to 1300 m), a result of intense benthic storms. The imprint of leakage from the Agulhas Current, identified through temperature and salinity, was observed in the upper water column profile of numerous particulate data (e.g. Pb, Ni, Cd). Measured elemental gradients, combined with measurements from a vertical mixing-profiler, will allow estimates of particulate fluxes to be calculated.

Possible Links Among Iron Reduction, Silicate Weathering, and Arsenic Mobility in the Mississippi River Alluvial Aquifer in Louisiana

NASA Astrophysics Data System (ADS)

Borrok, D. M.; Lenz, R. M.; Jennings, J. E.; Gentry, M. L.; Vinson, D. S.

2017-12-01

The Lower Mississippi River Alluvial Aquifer (LMRAA) is a critical groundwater resource for Arkansas, Mississippi, and Louisiana. Part of the aquifer in Louisiana contains waters rich in Na, HCO3, Fe, and As. We hypothesize that CO2 generated from dissimilatory iron reduction (DIR) within the aquifer acts to weather Na-bearing silicates, contributing Na and HCO3, which may influence the mobility of As. We examined the geochemistry of the aquifer using historical and new data collected from the Louisiana Department of Environmental Quality (LDEQ). Major and trace element data were collected from about 25 wells in the LMRAA in Louisiana every three years from 2001-2016. Samples collected in 2016 were additionally analyzed for water isotopes and the δ13C of dissolved inorganic carbon (DIC). Results suggest that groundwater in the LMRAA can be broken into two broad categories, (1) water with a molar Na/Cl ratio near 1 and/or high salinity, and (2) water with excess Na (i.e., the molar concentration of Na is greater than that of Cl) that is often higher in alkalinity (up to 616 mg/L as CaCO3), Fe (up to 21 mg/L), and sometimes As (up to 67 µg/L). Concentrations of dissolved Fe were found to correlate, at least weakly, with alkalinity and Na excess. Six of the approximately 25 wells historically sampled consistently had concentrations of As >10 µg/L. These locations generally correspond with groundwater characterized by higher Fe, alkalinity, and Na-excess. Initial results for δD and δ18O suggest that more isotopically depleted waters are sourced from the Mississippi River, whereas local precipitation recharges the aquifer farther from the river (δ18O ranged from -7.5‰ to -3.5‰). Part of the δ13C-DIC variation (-17.4‰ to -10.6‰) is consistent with pH modification (6.5-7.7) along differing horizontal and vertical flow paths in the aquifer. This geochemistry appears to be controlled in part by geology. Areas nearer to the current Mississippi River where alluvial valley train deposits are absent have thicker layers of Holocene-age clays, which may provide more labile organic matter for DIR, leading to higher concentrations of dissolved Fe in groundwater. Overall, these data are consistent with the hypothesized linkages among DIR, silicate weathering, and high (> 10µg/L) concentrations of As in parts of the LMRAA.

Opposing authigenic controls on the isotopic signature of dissolved iron in hydrothermal plumes

NASA Astrophysics Data System (ADS)

Lough, A. J. M.; Klar, J. K.; Homoky, W. B.; Comer-Warner, S. A.; Milton, J. A.; Connelly, D. P.; James, R. H.; Mills, R. A.

2017-04-01

Iron is a scarce but essential micronutrient in the oceans that limits primary productivity in many regions of the surface ocean. The mechanisms and rates of Fe supply to the ocean interior are still poorly understood and quantified. Iron isotope ratios of different Fe pools can potentially be used to trace sources and sinks of the global Fe biogeochemical cycle if these boundary fluxes have distinct signatures. Seafloor hydrothermal vents emit metal rich fluids from mid-ocean ridges into the deep ocean. Iron isotope ratios have the potential to be used to trace the input of hydrothermal dissolved iron to the oceans if the local controls on the fractionation of Fe isotopes during plume dispersal in the deep ocean are understood. In this study we assess the behaviour of Fe isotopes in a Southern Ocean hydrothermal plume using a sampling program of Total Dissolvable Fe (TDFe), and dissolved Fe (dFe). We demonstrate that δ56Fe values of dFe (δ56dFe) within the hydrothermal plume change dramatically during early plume dispersal, ranging from -2.39 ± 0.05‰ to -0.13 ± 0.06‰ (2 SD). The isotopic composition of TDFe (δ56TDFe) was consistently heavier than dFe values, ranging from -0.31 ± 0.03‰ to 0.78 ± 0.05‰, consistent with Fe oxyhydroxide precipitation as the plume samples age. The dFe present in the hydrothermal plume includes stabilised dFe species with potential to be transported to the deep ocean. We estimate that stable dFe exported from the plume will have a δ56Fe of -0.28 ± 0.17‰. Further, we show that the proportion of authigenic iron-sulfide and iron-oxyhydroxide minerals precipitating in the buoyant plume exert opposing controls on the resultant isotope composition of dissolved Fe passed into the neutrally buoyant plume. We show that such controls yield variable dissolved Fe isotope signatures under the authigenic conditions reported from modern vent sites elsewhere, and so ought to be considered during iron isotope reconstructions of past hydrothermalism from ocean sediment records.

Organic Exudates Enhance Iron Bioavailability to Trichodesmium (IMS101) by Modifying Fe Speciation

NASA Astrophysics Data System (ADS)

Tohidi Farid, H.; Rose, A.; Schulz, K.

2016-02-01

Although ferrous iron (Fe (II)) is believed to be the most readily absorbed form of Fe by cells, under alkaline and oxygenated conditions typical of marine environments, the thermodynamically stable Fe(III) state dominates. In marine environments, this Fe(III) is primarily presents as organic Fe(III)L complexes whose bioavailability is highly variable. However, it has been demonstrated that some eukaryotic marine algae are able to release organic ligands into their surrounding environments that change Fe bioavailability through complexation and/or redox reactions. Nevertheless, it is unclear how Fe(II) oxidation and Fe(III) reduction rates might be modified by these exudates and how this might increase or decrease iron bioavailability to microorganisms. Here, the role of natural organic ligands excreted by the cyanobacterium Trichodesmium erythraeum on the oxidation kinetics of Fe(II) was studied using the luminol chemiluminescence technique. The oxidation kinetics of Fe(II) were examined at nanomolar Fe concentrations in presence of different concentrations of EDTA and dissolved organic carbon exuded by Trichodesmium cells. The results indicated that an increase in the concentration of exuded organic matter, and consequently L:Fe(II) ratio, resulted in decreasing rates of Fe(II) oxidation by oxygen, primarily due to formation of Fe(II) complexes. Moreover, the results demonstrated that the exudates from Trichodesmium may be able to reduce Fe(III) to the more bioavailable Fe(II) state under some circumstances. This study therefore supports the ability of microorganisms to manipulate Fe bioavailability by releasing organic compounds into the extracellular environment that retard Fe(II) oxidation rates or reducing Fe(III) species to Fe(II). It also provides new insight into the potential mechanism(s) by which Trichdesmium may acquire Fe under conditions where Fe bioavailability is otherwise limited.

Soil Iron Content as a Predictor of Carbon and Nutrient Mobilization in Rewetted Fens

PubMed Central

Emsens, Willem-Jan; Aggenbach, Camiel J. S.; Schoutens, Ken; Smolders, Alfons J. P.; Zak, Dominik; van Diggelen, Rudy

2016-01-01

Rewetted, previously drained fens often remain sources rather than sinks for carbon and nutrients. To date, it is poorly understood which soil characteristics stimulate carbon and nutrient mobilization upon rewetting. Here, we assess the hypothesis that a large pool of iron in the soil negatively affects fen restoration success, as flooding-induced iron reduction (Fe3+ to Fe2+) causes a disproportionate breakdown of organic matter that is coupled with a release of inorganic compounds. We collected intact soil cores in two iron-poor and two iron-rich drained fens, half of which were subjected to a rewetting treatment while the other half was kept drained. Prolonged drainage led to the mobilization of nitrate (NO3-, > 1 mmol L-1) in all cores, regardless of soil iron content. In the rewetted iron-rich cores, a sharp increase in pore water iron (Fe) concentrations correlated with concentrations of inorganic carbon (TIC, > 13 mmol L-1) and dissolved organic carbon (DOC, > 16 mmol L-1). Additionally, ammonium (NH4+) accumulated up to phytotoxic concentrations of 1 mmol L-1 in the pore water of the rewetted iron-rich cores. Disproportionate mobilization of Fe, TIC, DOC and NH4+ was absent in the rewetted iron-poor cores, indicating a strong interaction between waterlogging and iron-mediated breakdown of organic matter. Concentrations of dissolved phosphorus (P) rose slightly in all cores upon rewetting, but remained low throughout the experiment. Our results suggest that large pools of iron in the top soil of drained fens can hamper the restoration of the fen’s sink-service for ammonium and carbon upon rewetting. We argue that negative effects of iron should be most apparent in fens with fluctuating water levels, as temporary oxygenation allows frequent regeneration of Fe3+. We conclude that rewetting of iron-poor fens may be more feasible for restoration. PMID:27050837

Interactions between magnetite and humic substances: redox reactions and dissolution processes.

PubMed

Sundman, Anneli; Byrne, James M; Bauer, Iris; Menguy, Nicolas; Kappler, Andreas

2017-10-19

Humic substances (HS) are redox-active compounds that are ubiquitous in the environment and can serve as electron shuttles during microbial Fe(III) reduction thus reducing a variety of Fe(III) minerals. However, not much is known about redox reactions between HS and the mixed-valent mineral magnetite (Fe 3 O 4 ) that can potentially lead to changes in Fe(II)/Fe(III) stoichiometry and even dissolve the magnetite. To address this knowledge gap, we incubated non-reduced (native) and reduced HS with four types of magnetite that varied in particle size and solid-phase Fe(II)/Fe(III) stoichiometry. We followed dissolved and solid-phase Fe(II) and Fe(III) concentrations over time to quantify redox reactions between HS and magnetite. Magnetite redox reactions and dissolution processes with HS varied depending on the initial magnetite and HS properties. The interaction between biogenic magnetite and reduced HS resulted in dissolution of the solid magnetite mineral, as well as an overall reduction of the magnetite. In contrast, a slight oxidation and no dissolution was observed when native and reduced HS interacted with 500 nm magnetite. This variability in the solubility and electron accepting and donating capacity of the different types of magnetite is likely an effect of differences in their reduction potential that is correlated to the magnetite Fe(II)/Fe(III) stoichiometry, particle size, and crystallinity. Our study suggests that redox-active HS play an important role for Fe redox speciation within minerals such as magnetite and thereby influence the reactivity of these Fe minerals and their role in biogeochemical Fe cycling. Furthermore, such processes are also likely to have an effect on the fate of other elements bound to the surface of Fe minerals.

Quantitative evaluation of the effect of H2O degassing on the oxidation state of magmas

NASA Astrophysics Data System (ADS)

Lange, R. A.; Waters, L.

2014-12-01

The extent to which degassing of the H2O component affects the oxidation state of hydrous magmas is widely debated. Several researchers have examined how degassing of mixed H-C-O-S-Cl fluids may change the Fe3+/FeT ratio of various magmas, whereas our focus is on the H2O component. There are two ways that degassing of H2O by itself may cause oxidation: (1) the reaction: H2O (melt) + 2FeO (melt) = H2 (fluid) + Fe2O3 (melt), and/or (2) if dissolved water preferentially enhances the activity of ferrous vs. ferric iron in magmatic liquids. In this study, a comparison is made between the pre-eruptive oxidation states of 14 crystal-poor, jet-black obsidian samples (obtained from two Fe-Ti oxides) and their post-eruptive values (analyzed with the Wilson 1960 titration method tested against USGS standards). The obsidians are from Medicine Lake (CA), Long Valley (CA), and the western Mexican arc; all have low FeOT (1.1-2.1 wt%), rendering their Fe2+/Fe3+ ratios highly sensitive to the possible effects of substantial H2O degassing. The Fe-Ti oxide thermometer/oxybarometer of Ghiorso and Evans, (2008) gave temperatures for the 14 samples that range for 720 to 940°C and ΔNNO values of -0.9 to +1.4. With temperature known, the plagioclase-liquid hygrometer was applied and show that ≤ 6.5 wt% H2O was dissolved in the melts prior to eruption. In addition, pre-eruptive Cl and S concentrations were constrained on the basis of apatite analyses (Webster et al., 2009) and sulfur concentrations needed for saturation with pyrrhotite (Clemente et al., 2004), respectively. Maximum pre-eruptive chlorine and sulfur contents are 6000 and 200 ppm, respectively. After eruption, the rhyolites lost nearly all of their volatiles. Our results indicate no detectable change between pre- and post-eruptive Fe2+ concentrations, with an average deviation of ± 0.1 wt % FeO. Although degassing of large concentrations of S and/or Cl may affect the oxidation state of magmas, at the pre-eruptive levels in these 14 rhyolitic magmas, no effect is detected. Therefore, it can be robustly concluded that degassing of substantial amounts of the H2O component (≤ 6.5 wt%), by itself, does not induce oxidation in erupted magmas, particularly those more iron-rich than rhyolites (e.g., arc basalts).

Effect of Dunaliella tertiolecta organic exudates on the Fe(II) oxidation kinetics in seawater.

PubMed

González, A G; Santana-Casiano, J M; González-Dávila, M; Pérez-Almeida, N; Suárez de Tangil, M

2014-07-15

The role played by the natural organic ligands excreted by the green algae Dunaliella tertiolecta on the Fe(II) oxidation rate constants was studied at different stages of growth. The concentration of dissolved organic carbon increased from 2.1 to 7.1 mg L(-1) over time of culture. The oxidation kinetics of Fe(II) was studied at nanomolar levels and under different physicochemical conditions of pH (7.2-8.2), temperature (5-35 °C), salinity (10-37), and dissolved organic carbon produced by cells (2.1-7.1 mg L(-1)). The experimental rate always decreased in the presence of organic exudates with respect to that in the control seawater. The Fe(II) oxidation rate constant was also studied in the context of Marcus theory, where ΔG° was 39.31-51.48 kJ mol(-1). A kinetic modeling approach was applied for computing the equilibrium and rate constants for Fe(II) and exudates present in solution, the Fe(II) speciation, and the contribution of each Fe(II) species to the overall oxidation rate constant. The best fit model took into account two acidity equilibrium constants for the Fe(II) complexing ligands with pKa,1=9.45 and pKa,2=4.9. The Fe(II) complexing constants were KFe(II)-LH=3×10(10) and KFe(II)-L=10(7), and the corresponding computed oxidation rates were 68±2 and 36±8 M(-1) min(-1), respectively.

The Distribution between the Dissolved and the Particulate Forms of 49 Metals across the Tigris River, Baghdad, Iraq

PubMed Central

Hamad, Samera Hussein; Schauer, James Jay; Shafer, Martin Merrill; Abed Al-Raheem, Esam; Satar, Hyder

2012-01-01

The distribution of dissolved and particulate forms of 49 elements was investigated along transect of the Tigris River (one of the major rivers of the world) within Baghdad city and in its major tributary (Diyala River) from 11 to 28 July 2011. SF-ICP-MS was used to measure total and filterable elements at 17 locations along the Tigris River transect, two samples from the Diyala River, and in one sample from the confluence of the two rivers. The calculated particulate forms were used to determine the particle-partition coefficients of the metals. No major changes in the elements concentrations down the river transect. Dissolved phases dominated the physical speciation of many metals (e.g., As, Mo, and Pt) in the Tigris River, while Al, Fe, Pb, Th, and Ti were exhibiting high particulate fractions, with a trend of particle partition coefficients of [Ti(40) > Th(35) > Fe(15) > Al(13) > Pb(4.5)] ∗ 106 L/kg. Particulate forms of all metals exhibited high concentrations in the Diyala River, though the partition coefficients were low due to high TSS (~270 mg/L). A comparison of Tigris with the major rivers of the world showed that Tigris quality in Baghdad is comparable to Seine River quality in Paris. PMID:23304083

Geochemical interactions between constituents in acidic groundwater and alluvium in an aquifer near Globe, Arizona

USGS Publications Warehouse

Stollenwerk, Kenneth G.

1994-01-01

Acidic water from a copper-mining area has contaminated an alluvial aquifer and stream near Globe, Arizona. The most contaminated groundwater has a pH of 3.3, and contains about 100 mmol/1 SO4, 50 mmol/1 Fe, 11 mmol/1 Al and 3 mmol/1 Cu. Reactions between alluvium and acidic groundwater were first evaluated in laboratory column experiments. A geochemical model was developed and used in the equilibrium speciation program, MINTEQA2, to simulate breakthrough curves for different constituents from the column. The geochemical model was then used to simulate the measured changes in concentration of aqueous constituents along a flow path in the aquifer.The pH was predominantly controlled by reaction with carbonate minerals. Where carbonates had been dissolved, adsorption of H+ by iron oxides was used to simulate pH. Acidic groundwater contained little or no dissolved oxygen, and most aqueous Fe was present as Fe(II). In the anoxic core of the plume, Fe(II) was oxidized by MnO2 to Fe(III), which then precipitated as Fe(OH)3. Attenuation of aqueous Cu, Co, Mn, Ni and Zn was a function of pH and could be quantitatively modeled with the diffuse-layer, surface complexation model in MINTEQA2. Aluminum precipitated as amorphous Al(OH)3 at pH < 4.7 and as AlOHSO4 at pH < 4.7. Aqueous Ca and SO4were close to equilibrium with gypsum.After the alluvium in the column had reached equilibrium with acidic groundwater, uncontaminated groundwater was eluted through the column to evaluate the effect of reactants on groundwater remediation. The concentration of Fe, Mn, Cu, Co, Ni and Zn rapidly decreased to the detection limits within a few pore volumes. All of the gypsum that had precipitated initially redissolved, resulting in elevated Ca and SO4concentrations for about 5 pore volumes. Aluminum and pH exhibited the most potential for continued adverse effects on groundwater quality. As H+ desorbed from Fe(OH)3, pH remained below 4.5 for more than 20 pore volumes, resulting in dissolution of AlOHSO4 and elevated aqueous Al.

Major and trace element partitioning between dissolved and particulate phases in Antarctic surface snow.

PubMed

Grotti, M; Soggia, F; Ardini, F; Magi, E

2011-09-01

In order to provide a new insight into the Antarctic snow chemistry, partitioning of major and trace elements between dissolved and particulate (i.e. insoluble particles, >0.45 μm) phases have been investigated in a number of coastal and inland snow samples, along with their total and acid-dissolvable (0.5% nitric acid) concentrations. Alkaline and alkaline-earth elements (Na, K, Ca, Mg, Sr) were mainly present in the dissolved phase, while Fe and Al were predominantly associated with the particulate matter, without any significant difference between inland and coastal samples. On the other hand, partitioning of trace elements depended on the sampling site position, showing a general decrease of the particulate fraction by moving from the coast to the plateau. Cd, Cu, Pb and Zn were for the most part in the dissolved phase, while Cr was mainly associated with the particulate fraction. Co, Mn and V were equally distributed between dissolved and particulate phases in the samples collected from the plateau and preferentially associated with the particulate in the coastal samples. The correlation between the elements and the inter-sample variability of their concentration significantly decreased for the plateau samples compared to the coastal ones, according to a change in the relative contribution of the metal sources and in good agreement with the estimated marine and crustal enrichment factors. In addition, samples from the plateau were characterised by higher enrichment factors of anthropogenic elements (Cd, Cr, Cu, Pb and Zn), compared to the coastal area. Finally, it was observed that the acid-dissolvable metal concentrations were generally lower than the total concentration values, showing that the acid treatment can dissolve only a given fraction of the metal associated with the particulate (<20% for iron and aluminium).

Increased concentrations of potassium in heartwood of trees in response to groundwater contamination

USGS Publications Warehouse

Vroblesky, D.A.; Yanosky, T.M.; Siegel, F.R.

1992-01-01

The wood of tuliptrees (Liriodendron tulipifera L.) growing above groundwater contamination from a hazardous-waste landfill in Maryland contained elevated concentrations of potassium (K). The groundwater contamination also contained elevated concentrations of dissolved K, as well as arsenic (As), cadmium (Cd), chloride (Cl), iron (Fe), manganese (Mn), zinc (Zn), and organic solvents. The dissolved K is derived from disposed smoke munitions. The excess K in the tuliptrees is concentrated in the heartwood, the part of the xylem most depleted in K in trees growing outside of the contamination. These data show that the uptake and translocation of K by tuliptrees can be strongly influenced by the availability of K in groundwater contamination and suggest the utility of this species as an areal indicator of groundwater contamination. ?? 1992 Springer-Verlag New York Inc.

Mass-size distribution and concentration of metals from personal exposure to arc welding fume in pipeline construction: a case report.

PubMed

Yang, Show-Yi; Lin, Jia-Ming; Young, Li-Hao; Chang, Ching-Wen

2018-04-07

We investigate exposure to welding fume metals in pipeline construction, which are responsible for severe respiratory problems. We analyzed air samples obtained using size-fractioning cascade impactors that were attached to the welders performing shielded metal and gas tungsten arc welding outdoors. Iron, aluminum, zinc, chromium, manganese, copper, nickel, and lead concentrations in the water-soluble (WS) and water-insoluble (WI) portions were determined separately, using inductively coupled plasma mass spectrometry. The mass-size distribution of welding fume matches a log-normal distribution with two modes. The metal concentrations in the welding fume were ranked as follows: Fe > Al > Zn > Cr > Mn > Ni > Cu > Pb. In the WS portion, the capacities of metals dissolving in water are correlated with the metal species but particle sizes. Particularly, Zn, Mn, and Pb exhibit relatively higher capacities than Cu, Cr, Al, Fe, and Ni. Exposure of the gas-exchange region of the lungs to WS metals were in the range of 4.9% to 34.6% of the corresponding metals in air by considering the particle-size selection in lungs, metal composition by particle size, and the capacities of each metal dissolving in water.

Geochemistry of Dissolved Trace Metals in the Waters of Bahia Magdalena, Baja California Sur, Pacific Coast, Mexico

NASA Astrophysics Data System (ADS)

Suresh Babu, S.

2016-12-01

Forty two samples were acquired from the surface and bottom water profiles along 5 transects spread over Bahia Magdalena lagoon, Baja California Sur to assess the behavior of trace metals in a high influenced upwelling region on the Pacific coast. To elaborate the fate of metals, also the physico-chemical parameters (pH, temperature, salinity, conductivity, dissolved oxygen). Determination of the concentrations of trace metals (Fe, Mn, Cr, Cu, Co, Pb, Ni, Zn, Cd As, Hg) were measured using Atomic absorption spectrometry. The results demonstrated high values of As, Ni and Co which is attributed to the local geology and phosphate deposits. Low values of Fe and Mn are attested to the oxic conditions of the lagoon which are responsible for the oxidation of Fe and Mn. The region witnesses raised temperatures (28.92ºC) and salinities of 35.2 PSU for its arid climatic conditions and high rates of evaporation. In general, the region presented minor quantities of dissolved trace metals due to dispersion and high intense interaction with the open sea. The results were also compared with other studies to understand the enrichment pattern in this side of the pacific coast which experiences various geothermal activities and upwelling phenomenon.

Dissolved and colloidal trace elements in the Mississippi River Delta outflow after Hurricanes Katrina and Rita

USGS Publications Warehouse

Shim, Moo-Joon; Swarzenski, Peter W.; Shiller, Alan M.

2012-01-01

The Mississippi River delta outflow region is periodically disturbed by tropical weather systems including major hurricanes, which can terminate seasonal bottom water hypoxia and cause the resuspension of shelf bottom sediments which could result in the injection of trace elements into the water column. In the summer of 2005, Hurricanes Katrina and Rita passed over the Louisiana Shelf within a month of each other. Three weeks after Rita, we collected water samples in the Mississippi River delta outflow, examining the distributions of trace elements to study the effect of Hurricanes Katrina and Rita. We observed limited stratification on the shelf and bottom waters that were no longer hypoxic. This resulted, for instance, in bottom water dissolved Mn being lower than is typically observed during hypoxia, but with concentrations still compatible with Mn–O2 trends previously reported. Interestingly, for no element were we able to identify an obvious effect of sediment resuspension on its distribution. In general, elemental distributions were compatible with previous observations in the Mississippi outflow system. Co and Re, which have not been reported for this system previously, showed behavior consistent with other systems: input for Co likely from desorption and conservative mixing for Re. For Cs, an element for which there is little information regarding its estuarine behavior, conservative mixing was also observed. Our filtration method, which allowed us to distinguish the dissolved (<0.02 μm) from colloidal (0.02–0.45 μm) phase, revealed significant colloidal fractions for Fe and Zn, only. For Fe, the colloidal phase was the dominant fraction and was rapidly removed at low salinity. Dissolved Fe, in contrast, persisted out to mid-salinities, being removed in a similar fashion to nitrate. This ability to distinguish the smaller Fe (likely dominantly organically complexed) from larger colloidal suspensates may be useful in better interpreting the bioavailablity of the Fe in estuarine systems.

Dissolved and colloidal trace elements in the Mississippi River delta outflow after Hurricanes Katrina and Rita

NASA Astrophysics Data System (ADS)

Shim, Moo-Joon; Swarzenski, Peter W.; Shiller, Alan M.

2012-07-01

The Mississippi River delta outflow region is periodically disturbed by tropical weather systems including major hurricanes, which can terminate seasonal bottom water hypoxia and cause the resuspension of shelf bottom sediments which could result in the injection of trace elements into the water column. In the summer of 2005, Hurricanes Katrina and Rita passed over the Louisiana Shelf within a month of each other. Three weeks after Rita, we collected water samples in the Mississippi River delta outflow, examining the distributions of trace elements to study the effect of Hurricanes Katrina and Rita. We observed limited stratification on the shelf and bottom waters that were no longer hypoxic. This resulted, for instance, in bottom water dissolved Mn being lower than is typically observed during hypoxia, but with concentrations still compatible with Mn-O2 trends previously reported. Interestingly, for no element were we able to identify an obvious effect of sediment resuspension on its distribution. In general, elemental distributions were compatible with previous observations in the Mississippi outflow system. Co and Re, which have not been reported for this system previously, showed behavior consistent with other systems: input for Co likely from desorption and conservative mixing for Re. For Cs, an element for which there is little information regarding its estuarine behavior, conservative mixing was also observed. Our filtration method, which allowed us to distinguish the dissolved (<0.02 μm) from colloidal (0.02-0.45 μm) phase, revealed significant colloidal fractions for Fe and Zn, only. For Fe, the colloidal phase was the dominant fraction and was rapidly removed at low salinity. Dissolved Fe, in contrast, persisted out to mid-salinities, being removed in a similar fashion to nitrate. This ability to distinguish the smaller Fe (likely dominantly organically complexed) from larger colloidal suspensates may be useful in better interpreting the bioavailablity of the Fe in estuarine systems.

Dissolved and Colloidal Trace Elements in the Mississippi River Delta Outflow after Hurricanes Katrina and Rita

NASA Astrophysics Data System (ADS)

Shim, M.; Swarzenski, P. W.; Shiller, A. M.

2010-12-01

The Mississippi River (MR) plays an important role as a major fluvial source of dissolved and particulate materials for the Gulf of Mexico (GOM). This region is periodically disturbed by tropical weather systems including major hurricanes. Such storms have the potential to stir up the normally stratified water column of the Louisiana Shelf and thus can serve as a mechanism for the abrupt termination of seasonal bottom water hypoxia. Additionally, strong tropical systems can cause the resuspension of shelf bottom sediments which could result in the injection of trace elements into the water column. In the summer of 2005, two major hurricanes, Katrina and Rita, passed over the Louisiana Shelf within a month of each other. Three weeks after Rita, we participated in a survey of the waters of the Mississippi River delta outflow, examining the distributions of trace elements (including Ba, Co, Cr, Cs, Cu, Fe, Mn, Ni, Re, U, V, and Zn) in a comparison with previous results in this area. We indeed observed that there was limited stratification on the shelf and that bottom waters were no longer hypoxic. This resulted, for instance, in bottom water dissolved Mn being lower than is typically observed during hypoxia, but with concentrations still compatible with Mn-O2 trends previously reported. Interestingly, for no element were we able to identify an obvious effect of sediment resuspension on its distribution. In general, elemental distributions were compatible with previous observations in the Mississippi outflow system. Co and Re, which have not been reported for this system previously, showed behavior consistent with other systems: input for Co likely from desorption and conservative mixing for Re. For Cs, an element for which there is little information regarding its estuarine behavior, conservative mixing was also observed. Our filtration method, which allowed us to distinguish the dissolved (<0.02 µm) from colloidal (0.02 - 0.45 µm) phase, revealed significant colloidal fractions for Fe and Zn, only. For Fe, the colloidal phase was the dominant fraction and was rapidly removed at low salinity. Dissolved Fe, in contrast, persisted out to mid-salinities, being removed in a similar fashion to nitrate. This ability to distinguish the smaller Fe (likely dominantly organically complexed) from larger colloidal suspensates may be useful in better interpreting the bioavailablity of the Fe in estuarine systems.

A hybrid treatment of ozonation with limestone adsorption processes for the removal of Fe2+ in groundwater: Fixed bed column study

NASA Astrophysics Data System (ADS)

Akbar, Nor Azliza; Aziz, Hamidi Abdul; Adlan, Mohd Nordin

2017-10-01

During pumping of groundwater to the surface, the reaction between dissolved iron (Fe2+) and oxygen causes oxidation to ferric iron (Fe3+), thereby increasing the concentration of Fe2+. In this research, the potential application of ozonation with limestone adsorption to remove Fe2+ from groundwater was investigated through batch ozonation and fixed-bed-column studies. Groundwater samples were collected from a University Science Malaysia tube well (initial concentration of Fe2+, Co=1.563 mg/L). The effect of varying ozone dosages (10, 12.5, 15, 17.5, 20, 22.5, and 25 g/Nm3) was analyzed to determine the optimum ozone dosage for treatment. The characteristics of the column data and breakthrough curve were analyzed and predicted using mathematical models, such as Adam Bohart, Thomas, and Yoon-Nelson models. The data fitted well to the Thomas and Yoon-Nelson models, with correlation coefficient r2>0.93, but not to the Adam Bohart (r2=0.47). The total Fe2+ removed was 72% (final concentration of Fe2+, Ct=0.426 mg/L) at the maximum dosage of 25 g/Nm3 through ozonation only. However, the efficiency of Fe2+ removal was increased up to 99.5% (Ct=0.008 mg/L) when the hybrid treatment of ozonation with limestone adsorption was applied in this study. Thus, this integrated treatment was considerably more effective in removing Fe2+ than single ozonation treatment.

Establishing the environmental risk of metal contaminated river bank sediments

NASA Astrophysics Data System (ADS)

Lynch, Sarah; Batty, Lesley; Byrne, Patrick

2016-04-01

Climate change predictions indicate an increase in the frequency and duration of flood events along with longer dry antecedent conditions, which could alter patterns of trace metal release from contaminated river bank sediments. This study took a laboratory mesocosm approach. Chemical analysis of water and sediment samples allowed the patterns of Pb and Zn release and key mechanisms controlling Pb and Zn mobility to be determined. Trace metal contaminants Pb and Zn were released throughout flooded periods. The highest concentrations of dissolved Pb were observed at the end of the longest flood period and high concentrations of dissolved Zn were released at the start of a flood. These concentrations were found to exceed environmental quality standards. Key mechanisms controlling mobility were (i) evaporation, precipitation and dissolution of Zn sulphate salts, (ii) anglesite solubility control of dissolved Pb, (iii) oxidation of galena and sphalerite, (iv) reductive dissolution of Mn/Fe hydroxides and co-precipitation/adsorption with Zn. In light of climate change predictions these results indicate future scenarios may include larger or more frequent transient 'pulses' of dissolved Pb and Zn released to river systems. These short lived pollution episodes could act as a significant barrier to achieving the EU Water Framework Directive objectives.

Influence of dissolved organic matter on photogenerated reactive oxygen species and metal-oxide nanoparticle toxicity.

PubMed

Li, Yang; Niu, Junfeng; Shang, Enxiang; Crittenden, John Charles

2016-07-01

The effect of humic acid (HA) or fulvic acid (FA) on reactive oxygen species (ROS) generation by six metal-oxide nanoparticles (NPs) and their toxicities toward Escherichia coli was investigated under UV irradiation. Dissolved organic matter (DOM) decreased OH generation by TiO2, ZnO, and Fe2O3, with FA inhibiting OH generation more than HA. The generated OH in NPs/DOM mixtures was higher than the measured concentrations because DOM consumes OH faster than its molecular probe. None of NPs/FA mixtures produced O2(-). The generated O2(-) concentrations in NPs/HA mixtures (except Fe2O3/HA) were higher than the sum of O2(-) concentrations that produced as NPs and HA were presented by themselves. Synergistic O2(-) generation in NPs/HA mixtures resulted from O2 reduction by electron transferred from photoionized HA to NPs. DOM increased (1)O2 generation by TiO2, CuO, CeO2, and SiO2, and FA promoted (1)O2 generation more than HA. Enhanced (1)O2 generation resulted from DOM sensitization of NPs. HA did not increase (1)O2 generation by ZnO and Fe2O3 primarily because released ions quenched (1)O2 precursor ((3)HA*). Linear correlation was developed between total ROS concentrations generated by NPs/DOM mixtures and bacterial survival rates (R(2) ≥ 0.80). The results implied the necessity of considering DOM when investigating the photoreactivity of NPs. Copyright © 2016 Elsevier Ltd. All rights reserved.

Effects of molecular composition of natural organic matter on ferric iron complexation at circumneutral pH.

PubMed

Fujii, Manabu; Imaoka, Akira; Yoshimura, Chihiro; Waite, T D

2014-04-15

Thermodynamic and kinetic parameters for ferric iron (Fe[III]) complexation by well-characterized humic substances (HS) from various origins were determined by a competitive ligand method with 5-sulfosalicylic acid at circumneutral pH (6.0-8.0) and an ionic strength of ∼0.06 M. The measured Fe binding properties including conditional stability constants and complexation capacities ranged over more than 2 orders of magnitude, depending on the origin and the particular operationally defined fraction of HS examined. Statistical comparison of the complexation parameters to a range of chemical properties of the HS indicated a strong positive correlation between Fe(III) complexation capacity and aromatic carbon content in the HS at all pHs examined. In contrast, the complexation capacity was determined to be up to a few orders of magnitude smaller than the concentration of carboxylic and phenolic groups present. Therefore, specific functional groups including those resident in the proximity of aromatic structures within the HS are likely preferable for Fe(III) coordination under the conditions examined. Overall, our results suggest that the concentration of dissolved Fe(III) complexes in natural waters is substantially influenced by variation in HS characteristics in addition to other well-known factors such as HS concentration and nature and concentration of competing cations present.

Size and elemental distributions of nano- to micro-particulates in the geochemically-stratified Great Salt Lake

USGS Publications Warehouse

Diaz, X.; Johnson, W.P.; Fernandez, D.; Naftz, D.L.

2009-01-01

The characterization of trace elements in terms of their apportionment among dissolved, macromolecular, nano- and micro-particulate phases in the water column of the Great Salt Lake carries implications for the potential entry of toxins into the food web of the lake. Samples from the anoxic deep and oxic shallow brine layers of the lake were fractionated using asymmetric flow field-flow fractionation (AF4). The associated trace elements were measured via online collision cell inductively-coupled plasma mass spectrometry (CC-ICP-MS). Results showed that of the total (dissolved + particulate) trace element mass, the percent associated with particulates varied from negligible (e.g. Sb), to greater than 50% (e.g. Al, Fe, Pb). Elements such as Cu, Zn, Mn, Co, Au, Hg, and U were associated with nanoparticles, as well as being present as dissolved species. Particulate-associated trace elements were predominantly associated with particulates larger than 450 nm in size. Among the smaller nanoparticulates (<450 nm), some trace elements (Ni, Zn, Au and Pb) showed higher percent mass (associated with nanoparticles) in the 0.9-7.5 nm size range relative to the 10-250 nm size range. The apparent nanoparticle size distributions were similar between the two brine layers; whereas, important differences in elemental associations to nanoparticles were discerned between the two layers. Elements such as Zn, Cu, Pb and Mo showed increasing signal intensities from oxic shallow to anoxic deep brine, suggesting the formation of sulfide nanoparticles, although this may also reflect association with dissolved organic matter. Aluminum and Fe showed greatly increased concentration with depth and equivalent size distributions that differed from those of Zn, Cu, Pb and Mo. Other elements (e.g. Mn, Ni, and Co) showed no significant change in signal intensity with depth. Arsenic was associated with <2 nm nanoparticles, and showed no increase in concentration with depth, possibly indicating dissolved arsenite. Mercury was associated with <2 nm nanoparticles, and showed greatly increased concentration with depth, possibly indicating association with dissolved organic matter. ?? 2009 Elsevier Ltd.

Oxidation of Fe(II) in rainwater.

PubMed

Willey, J D; Whitehead, R F; Kieber, R J; Hardison, D R

2005-04-15

Photochemically produced Fe(II) is oxidized within hours under environmentally realistic conditions in rainwater. The diurnal variation between photochemical production and reoxidation of Fe(II) observed in our laboratory accurately mimics the behavior of ferrous iron observed in field studies where the highest concentrations of dissolved Fe(ll) occur in afternoon rain during the period of maximum sunlight intensity followed by gradually decreasing concentrations eventually returning to early morning pre-light values. The experimental work presented here, along with the results of kinetics studies done by others, suggests thatthe primary process responsible for the decline in photochemically produced Fe(II) concentrations is oxidation by hydrogen peroxide. This reaction is first order with respect to both the concentrations of Fe(II) and H2O2. The second-order rate constant determined for six different authentic rain samples varied over an order of magnitude and was always less than or equal to the rate constant determined for this reaction in simple acidic solutions. Oxidation of photochemically produced ferrous iron by other oxidants including molecular oxygen, ozone, hydroxyl radical, hydroperoxyl/superoxide radical, and hexavalent chromium were found to be insignificant under the conditions present in rainwater. This study shows that Fe(II) occurs as at least two different chemical species in rain; photochemically produced Fe(II) that is oxidized over time periods of hours, and a background Fe(II) that is protected against oxidation, perhaps by organic complexation, and is stable against oxidation for days. Because the rate of oxidation of photochemically produced Fe(II) does not increase with increasing rainwater pH, the speciation of this more labile form of Fe(II) is also not controlled by simple hydrolysis reactions.

Influence of uranyl speciation and iron oxides on uranium biogeochemical redox reactions

DOE Office of Scientific and Technical Information (OSTI.GOV)

Stewart, B.D.; Amos, R.T.; Nico, P.S.

2010-03-15

Uranium is a pollutant of concern to both human and ecosystem health. Uranium's redox state often dictates its partitioning between the aqueous- and solid-phases, and thus controls its dissolved concentration and, coupled with groundwater flow, its migration within the environment. In anaerobic environments, the more oxidized and mobile form of uranium (UO{sub 2}{sup 2+} and associated species) may be reduced, directly or indirectly, by microorganisms to U(IV) with subsequent precipitation of UO{sub 2}. However, various factors within soils and sediments may limit biological reduction of U(VI), inclusive of alterations in U(VI) speciation and competitive electron acceptors. Here we elucidate themore » impact of U(VI) speciation on the extent and rate of reduction with specific emphasis on speciation changes induced by dissolved Ca, and we examine the impact of Fe(III) (hydr)oxides (ferrihydrite, goethite and hematite) varying in free energies of formation on U reduction. The amount of uranium removed from solution during 100 h of incubation with S. putrefaciens was 77% with no Ca or ferrihydrite present but only 24% (with ferrihydrite) and 14% (no ferrihydrite) were removed for systems with 0.8 mM Ca. Imparting an important criterion on uranium reduction, goethite and hematite decrease the dissolved concentration of calcium through adsorption and thus tend to diminish the effect of calcium on uranium reduction. Dissimilatory reduction of Fe(III) and U(VI) can proceed through different enzyme pathways, even within a single organism, thus providing a potential second means by which Fe(III) bearing minerals may impact U(VI) reduction. We quantify rate coefficients for simultaneous dissimilatory reduction of Fe(III) and U(VI) in systems varying in Ca concentration (0 to 0.8 mM), and using a mathematical construct implemented with the reactive transport code MIN3P, we reveal the predominant influence of uranyl speciation, specifically the formation of uranyl-calcium-carbonato complexes, and ferrihydrite on the rate and extent of uranium reduction in complex geochemical systems.« less

Evolution of concentration-discharge relations revealed by high frequency diurnal sampling of stream water during spring snowmelt

NASA Astrophysics Data System (ADS)

Olshansky, Y.; White, A. M.; Thompson, M.; Moravec, B. G.; McIntosh, J. C.; Chorover, J.

2017-12-01

Concentration discharge (C-Q) relations contain potentially important information on critical zone (CZ) processes including: weathering reactions, water flow paths and nutrient export. To examine the C-Q relations in a small (3.3 km2) headwater catchment - La Jara Creek located in the Jemez River Basin Critical Zone Observatory, daily, diurnal stream water samples were collected during spring snow melt 2017, from two flumes located in outlets of the La Jara Creek and a high elevation zero order basin within this catchment. Previous studies from this site (McIntosh et al., 2017) suggested that high frequency sampling was needed to improve our interpretation of C-Q relations. The dense sampling covered two ascending and two descending limbs of the snowmelt hydrograph, from March 1 to May 15, 2017. While Na showed inverse correlation (dilution) with discharge, most other solutes (K, Mg, Fe, Al, dissolved organic carbon) exhibited positive (concentration) or chemostatic trends (Ca, Mn, Si, dissolved inorganic carbon and dissolved nitrogen). Hysteresis in the C-Q relation was most pronounced for bio-cycled cations (K, Mg) and for Fe, which exhibited concentration during the first ascending limb followed by a chemostatic trend. A pulsed increase in Si concentration immediately after the first ascending limb in both flumes suggests mixing of deep groundwater with surface water. A continual increase in Ge/Si concentrations followed by a rapid decrease after the second rising limb may suggest a fast transition between soil water to ground water dominating the stream flow. Fourier transform infrared spectroscopy of selected samples across the hydrograph demonstrated pronounced changes in dissolved organic matter molecular composition with the advancement of the spring snow melt. X-ray micro-spectroscopy of colloidal material isolated from the collected water samples indicated a significant role for organic matter in the transport of inorganic colloids. Analyses of high frequency diurnal sampling greatly improve our ability to probe rapid CZ changes occurring during spring snowmelt, and provide useful information for evaluation and modeling of CZ processes in other snow melt dominated regions.

Simplified sample treatment for the determination of total concentrations and chemical fractionation forms of Ca, Fe, Mg and Mn in soluble coffees.

PubMed

Pohl, Pawel; Stelmach, Ewelina; Szymczycha-Madeja, Anna

2014-11-15

A simpler, and faster than wet digestion, sample treatment was proposed prior to determination of total concentrations for selected macro- (Ca, Mg) and microelements (Fe, Mn) in soluble coffees by flame atomic absorption spectrometry. Samples were dissolved in water and acidified with HNO3. Precision was in the range 1-4% and accuracy was better than 2.5%. The method was used in analysis of 18 soluble coffees available on the Polish market. Chemical fractionation patterns for Ca, Fe, Mg and Mn in soluble coffees, as consumed, using a two-column solid-phase extraction method, determined Ca, Mg and Mn were present predominantly as cations (80-93% of total content). This suggests these elements are likely to be highly bioaccessible. Copyright © 2014 Elsevier Ltd. All rights reserved.

Low temperature hydrogen production during experimental hydration of partially-serpentinized dunite

NASA Astrophysics Data System (ADS)

Miller, Hannah M.; Mayhew, Lisa E.; Ellison, Eric T.; Kelemen, Peter; Kubo, Mike; Templeton, Alexis S.

2017-07-01

Dissolved hydrogen is common in mafic and ultramafic aquifers; however, the water/rock reactions that give rise to hydrogen production at near-surface temperatures are enigmatic. Similarly, mineral hydration experiments have not yet unequivocally demonstrated whether H2 can be produced at low-temperatures at significant rates from reaction of aqueous fluids with basalts and peridotites for prolonged amounts of time. We conducted laboratory-based water/rock reactions between partially serpentinized Oman dunite and a simulated Oman rainwater (RW) media, as well as a simulated seawater (SW) media, to quantify H2 generation rates at 100 °C. Throughout more than 9 months of water/rock reaction, extensive hydrogen production and consumption were observed in RW and SW media. In the first 24 h of reaction in anoxic fluids containing only dissolved N2 and CO2, the room-temperature pH in both RW and SW media increased from 6.5 to ∼9, and the average pH then remained relatively constant at pH 8.5 (±0.5 pH) for the duration of the experiments. We also measured some of the highest hydrogen concentrations observed in experimental low-temperature serpentinization reactions. The maximum measured H2 concentrations in SW media were 470 nmol H2 per g mineral after ∼3 months, while RW media H2 concentrations reached 280 nmol/g H2 after ∼3 months. After reaching micromolar dissolved H2(aq), the H2 concentrations notably declined, and CO2 was almost fully consumed. We measured the formation of formate (up to 98 μM) and acetate (up to 91 μM) associated with a drawdown of H2 and CO2 in the experiments. No CH4 or carbonate formation was observed. To identify reactions giving rise to low-temperature hydrogen production, the mineralogy and oxidation state of the Fe-bearing species in the dunite were extensively characterized before and after reaction using Raman spectroscopy, Quantitative Evaluation of Minerals by SCANing electron microscopy (QEMSCAN), powder X-ray diffraction (XRD), magnetic susceptibility, scanning electron microscopy (SEM), and Fe K-edge X-ray absorption near edge structure (XANES) spectroscopic techniques. The mineralogy of the solid starting material was dominated by olivine and serpentine with minor brucite, pyroxene and spinel. After reaction, additional serpentine and magnetite could be detected as reaction products, and pre-existing brucite was consumed. No changes were observed in the abundance or grain sizes of olivine or pyroxene. Thus, we propose that the destabilization of Fe(II)-bearing brucite and the subsequent oxidation of the aqueous Fe(II) to form magnetite and Fe(III)-rich serpentine give rise to H2 production at 100 °C. This work demonstrates that dissolved hydrogen and low molecular weight organic acids can be produced by the reaction of labile Fe(II)-bearing minerals generated during a prior stage of water/rock reactions. In particular, progressive alteration of partially-serpentinized peridotites containing brucite may generate sufficient electron donors to fuel in-situ subsurface microbial activity.

Phosphorus Release to Floodwater from Calcareous Surface Soils and Their Corresponding Subsurface Soils under Anaerobic Conditions.

PubMed

Jayarathne, P D K D; Kumaragamage, D; Indraratne, S; Flaten, D; Goltz, D

2016-07-01

Enhanced phosphorus (P) release from soils to overlying water under flooded, anaerobic conditions has been well documented for noncalcareous and surface soils, but little information is available for calcareous and subsurface soils. We compared the magnitude of P released from 12 calcareous surface soils and corresponding subsurface soils to overlying water under flooded, anaerobic conditions and examined the reasons for the differences. Surface (0-15 cm) and subsurface (15-30 cm) soils were packed into vessels and flooded for 8 wk. Soil redox potential and concentrations of dissolved reactive phosphorus (DRP) and total dissolved Ca, Mg, Fe, and Mn in floodwater and pore water were measured weekly. Soil test P was significantly smaller in subsurface soils than in corresponding surface soils; thus, the P release to floodwater from subsurface soils was significantly less than from corresponding surface soils. Under anaerobic conditions, floodwater DRP concentration significantly increased in >80% of calcareous surface soils and in about 40% of subsurface soils. The increase in floodwater DRP concentration was 2- to 17-fold in surface soils but only 4- to 7-fold in subsurface soils. With time of flooding, molar ratios of Ca/P and Mg/P in floodwater increased, whereas Fe/P and Mn/P decreased, suggesting that resorption and/or reprecipitation of P took place involving Fe and Mn. Results indicate that P release to floodwater under anaerobic conditions was enhanced in most calcareous soils. Surface and subsurface calcareous soils in general behaved similarly in releasing P under flooded, anaerobic conditions, with concentrations released mainly governed by initial soil P concentrations. Copyright © by the American Society of Agronomy, Crop Science Society of America, and Soil Science Society of America, Inc.

Estimates of atmospheric O2 in the Paleoproterozoic from paleosols

NASA Astrophysics Data System (ADS)

Kanzaki, Yoshiki; Murakami, Takashi

2016-02-01

A weathering model was developed to constrain the partial pressure of atmospheric O2 (PO2) in the Paleoproterozoic from the Fe records in paleosols. The model describes the Fe behavior in a weathering profile by dissolution/precipitation of Fe-bearing minerals, oxidation of dissolved Fe(II) to Fe(III) by oxygen and transport of dissolved Fe by water flow, in steady state. The model calculates the ratio of the precipitated Fe(III)-(oxyhydr)oxides from the dissolved Fe(II) to the dissolved Fe(II) during weathering (ϕ), as a function of PO2 . An advanced kinetic expression for Fe(II) oxidation by O2 was introduced into the model from the literature to calculate accurate ϕ-PO2 relationships. The model's validity is supported by the consistency of the calculated ϕ-PO2 relationships with those in the literature. The model can calculate PO2 for a given paleosol, once a ϕ value and values of the other parameters relevant to weathering, namely, pH of porewater, partial pressure of carbon dioxide (PCO2), water flow, temperature and O2 diffusion into soil, are obtained for the paleosol. The above weathering-relevant parameters were scrutinized for individual Paleoproterozoic paleosols. The values of ϕ, temperature, pH and PCO2 were obtained from the literature on the Paleoproterozoic paleosols. The parameter value of water flow was constrained for each paleosol from the mass balance of Si between water and rock phases and the relationships between water saturation ratio and hydraulic conductivity. The parameter value of O2 diffusion into soil was calculated for each paleosol based on the equation for soil O2 concentration with the O2 transport parameters in the literature. Then, we conducted comprehensive PO2 calculations for individual Paleoproterozoic paleosols which reflect all uncertainties in the weathering-relevant parameters. Consequently, robust estimates of PO2 in the Paleoproterozoic were obtained: 10-7.1-10-5.4 atm at ∼2.46 Ga, 10-5.0-10-2.5 atm at ∼2.15 Ga, 10-5.2-10-1.7 atm at ∼2.08 Ga and more than 10-4.6-10-2.0 atm at ∼1.85 Ga. Comparison of the present PO2 estimates to those in the literature suggests that a drastic rise of oxygen would not have occurred at ∼2.4 Ga, supporting a slightly rapid rise of oxygen at ∼2.4 Ga and a gradual rise of oxygen in the Paleoproterozoic in long term.

Oxygen and superoxide-mediated redox kinetics of iron complexed by humic substances in coastal seawater.

PubMed

Fujii, Manabu; Rose, Andrew L; Waite, T David; Omura, Tatsuo

2010-12-15

Complexes with terrestrially derived humic substances represent one of the most reactive pools of dissolved Fe in natural waters. In this work, redox kinetics of Fe-humic substance complexes (FeL) in simulated coastal seawater were investigated using chemiluminescence techniques with particular attention given to interactions with dioxygen (O2) and superoxide (O2•-). Although rate constants of FeIIL oxidation by O2 (5.6-52 M-1 · s-1) were 4-5 orders of magnitude less than those for O2•- (6.9-23 × 105 M-1 · s-1),O2 is likely to outcompete O2•- for FeIIL oxidation in coastal seawaters where steady-state O2•- concentrations are generally subnanomolar. Rate constants for FeIIIL reduction by O2•- of 1.8-5.6 × 104 M-1 · s-1 were also determined. From the balance of FeIIL oxidation rates and O2•- -mediated FeIIIL reduction rates, steady-state FeIIL concentrations were estimated to be in the subpicomolar to picomolar range, which is generally lower than measured in situ Fe(II) concentrations under relevant conditions. This suggests that (i) processes other than O2•- -mediated reduction (such as photochemical ligand-to-metal charge transfer) may be responsible for Fe(II) formation, (ii) the in situ ligands differ significantly from the humic substances used in this work, and/ or (iii) the influence of other environmental factors such as pH and temperature on Fe redox kinetics may have to be considered.

Occurrence and photodegradation of methylmercury in surface water of Wen-Rui-Tang River network, Wenzhou, China.

PubMed

Pan, Shuihong; Feng, Chuchu; Lin, Jialu; Cheng, Lidong; Wang, Chengjun; Zuo, Yuegang

2017-04-01

The spatial distribution and seasonal variations of methylmercury (MeHg) in Wen-Rui-Tang (WRT) River network were investigated by monitoring the MeHg concentrations in surface water samples collected from 30 sites across the river network over four seasons. Detection frequencies and concentrations of MeHg were generally higher in January, indicating that low sunlight irradiation, wind speed, and temperature conditions might enhance the persistence of MeHg in surface water. The MeHg levels varied with sampling locations, with the highest concentrations being observed in the industrial area especially around wastewater outfall, revealing that the mercury contamination in WRT River mainly comes from the industrial wastewater. Photodegradation of MeHg in WRT River surface water and the effects of natural constituents such as fulvic acid (FA), ferric ions (Fe 3+ ), nitrate (NO 3 - ), and dissolved oxygen on the MeHg photodegradation in aqueous solutions were studied under the simulated sunlight. The experimental data indicated that the indirect photodecomposition of MeHg occurred in WRT River surface water. Photodegradation of MeHg in FA solution was initiated by triplet 3 FA* or MeHg-FA* via electron transfer interaction under light irradiations. The Fe 3+ and NO 3 - can absorb light energy to produce ·OH and enhance the photochemical degradation of MeHg. The MeHg photodecompositions in FA, nitrate, and Fe 3+ solutions were markedly accelerated after removing the dissolved oxygen.

A Re-evaluation of the Ferrozine Method for Dissolved Iron: The Effect of Organic Interferences

NASA Astrophysics Data System (ADS)

Balind, K.; Barber, A.; Gelinas, Y.

2016-12-01

Among the most commonly used analytical methods in geochemistry is the ferrozine method for determining dissolved iron concentration in water (1). This cheap and easy-to-use spectrophotometric method involves a complexing agent (ferrozine), a reducing agent (hydroxylamine-HCl) and buffer (ammonium acetate with ammonium hydroxide). Previous studies have demonstrated that complex organic matter (OM) originating from the Suwannee River did not lead to a significantly underestimation of the measured iron content in OM amended iron solutions (2). The authors concluded that this method could be used even in organic rich (i.e., 25 mg/L) waters. Here we compare the concentration of Fe measured using this spectrophotometric method to the total Fe as measured by ICP-MS in the presence/absence of specific organic molecules to ascertain if they interfere with the ferrozine method. We show that certain molecules with hydroxyl and carboxyl functional groups as well as multi-dentate chelating species have a significant effect on the measured iron concentrations. Two possible mechanisms likely are responsible for the inefficiency of this method in the presence of specific organic molecules; 1) incomplete reduction of Fe(III) bound to organic molecules, or 2) competition between the OM and ferrozine for the available iron. We address these possibilities separately by varying the experimental conditions. These methodological artifacts may have far reaching implications due to the extensive use of this method. Stookey, L. L., Anal. Chem., 42, 779 (1970). Viollier, E., et al., Applied Geochem., 15, 785 (2000).

DOE Office of Scientific and Technical Information (OSTI.GOV)

Harriman, D.A.; Sargent, B.P.

Groundwater quality was evaluated in seven confined aquifers and the water table aquifer in east-central New Jersey based on 237 analyses of samples collected in 1981-82, and 225 older analyses. Investigation of the effect of land use on water quality and several sampling network proposals for the region are reported. Iron (Fe) and manganese (Mn) concentrations exceed US EPA drinking water standards in some wells screened in the Potomac-Raritan-Magothy aquifer system. Sodium (Na) concentrations in samples from three wells more than 800 ft deep in the Englishtown aquifer exceed the standard. Iron and Mn concentrations in this aquifer may alsomore » exceed the standards. Iron concentrations in the Wenonah-Mount Laurel aquifer exceed the standard. Based on 15 analyses of water from the Vincetown aquifer, Mn is the only constituent that exceeds the drinking water standard. In the Manasquan aquifer, 4 of the 16 Na determinations exceed the standard, and 8 of 16 Fe determinations exceed the standard. Water quality in the Atlantic City 800-ft sand is generally satisfactory. However, 12 Fe and 1 of 12 Mn determinations exceed the standards. For the Rio Grande water-bearing zone, 1 of 3 Fe determinations exceed the standard. The Kirkwood-Cohansey aquifer system was the most thoroughly sampled (249 chemical analyses from 209 wells). Dissolved solids, chloride, Fe, nitrate, and Mn concentrations exceed drinking water standards in some areas. 76 refs., 36 figs., 12 tabs.« less

The Effect of Ion Adsorption on Microbial Dissimilatory Iron-Reduction and the Mobility of Adsorbed As(V)

NASA Astrophysics Data System (ADS)

Meyer, B. A.; Stillings, L. L.

2003-12-01

The effect of varying environmental conditions on the microbial reduction of Fe(III) and the mobility of adsorbed As(V) was investigated by studying the kinetics of reductive dissolution of synthetic, hydrous ferric oxide (HFO) in three batch-reactor experiments. Growth medium, containing HFO as an electron acceptor (EA) and acetate as an electron donor (ED), was dispensed into 500-ml septum sealed serum bottles. Each bottle was inoculated with an enrichment culture (MEC) containing an anaerobic Fe-reducing bacterium obtained from sediments at Milltown Reservoir near Missoula, MT. Each enrichment culture grew for at least 600 hrs and exhibited both exponential and stationary growth. Microbial reduction was monitored by measuring the production of dissolved Fe(II). Total Fe(II) was calculated by applying a Langmuir adsorption model, developed for each growth condition, to the measured dissolved Fe(II). Total Fe(II) production was modeled by: x = Xs(1-e-ket)-[kL(e-ket)]+(kL/ke) where x is the total Fe(II) concentration (mM) at t, ke is the exponential production rate constant (hr-1), Xs is the total Fe(II) concentration (mM) at the time of transition between exponential and stationary growth, t is the time since inoculation minus lag time, and kL is the stationary (linear) production rate constant (mM hr-1). From our experiments we learned that: 1) increasing the concentration of EA from 10-30 mM had no effect on the value of ke, which remained constant at 0.015 hr-1. However, the maximum production rate, Rmax = (ke Xs)+kL, did increase with increasing EA, varying from 0.014-0.031 mM hr-1; 2) increasing the concentration of ED from 10-30 mM had no effect on either ke or Rmax. These values remained constant as ED increased; 3) sorption of As(V) to the EA (in mM ratios of 1:10 and 1:30, As(V):HFO) affected Rmax but not ke. Rmax increased with increasing EA, as observed earlier, but its value was lower than in cultures without arsenic. In the presence of As(V), Rmax was unaffected by increasing ED. Microbial reduction of EA did not result in the release of aqueous As(V) or As(III). In all cases, representative blank and kill controls were run concurrent with growth experiments. No Fe(II) production was observed in the controls. The modeling method showed that increases in Rmax, when observed, were due to an elongated exponential growth phase. We conclude that the availability of surface sites to the culture is the controlling factor in microbial iron reduction. The length of the exponential growth phase depends on the concentration of surface sites available for microbial reduction. Adsorbed Fe(II) or As(V) inhibits reduction by decreasing the concentration of available surface sites. Likewise, increasing the initial concentration of EA increases the concentration of available surface sites thus increasing Rmax.

Anoxic nitrate reduction coupled with iron oxidation and attenuation of dissolved arsenic and phosphate in a sand and gravel aquifer

USGS Publications Warehouse

Smith, Richard L.; Kent, Douglas B.; Repert, Deborah A.; Böhlke, J.K.

2017-01-01

Nitrate has become an increasingly abundant potential electron acceptor for Fe(II) oxidation in groundwater, but this redox couple has not been well characterized within aquifer settings. To investigate this reaction and some of its implications for redox-sensitive groundwater contaminants, we conducted an in situ field study in a wastewater-contaminated aquifer on Cape Cod. Long-term (15 year) geochemical monitoring within the contaminant plume indicated interacting zones with variable nitrate-, Fe(II)-, phosphate-, As(V)-, and As(III)-containing groundwater. Nitrate and phosphate were derived predominantly from wastewater disposal, whereas Fe(II), As(III), and As(V) were mobilized from the aquifer sediments. Multiple natural gradient, anoxic tracer tests were conducted in which nitrate and bromide were injected into nitrate-free, Fe(II)-containing groundwater. Prior to injection, aqueous Fe(II) concentrations were approximately 175 μM, but sorbed Fe(II) accounted for greater than 90% of the total reactive Fe(II) in the aquifer. Nitrate reduction was stimulated within 1 m of transport for 100 μM and 1000 μM nitrate additions, initially producing stoichiometric quantities of nitrous oxide (>300 μM N). In subsequent injections at the same site, nitrate was reduced even more rapidly and produced less nitrous oxide, especially over longer transport distances. Fe(II) and nitrate concentrations decreased together and were accompanied by Fe(III) oxyhydroxide precipitation and decreases in dissolved phosphate, As(III), and As(V) concentrations. Nitrate N and O isotope fractionation effects during nitrate reduction were approximately equal (ε15N/ε18O = 1.11) and were similar to those reported for laboratory studies of biological nitrate reduction, including denitrification, but unlike some reported effects on nitrate by denitrification in aquifers. All constituents affected by the in situ tracer experiments returned to pre-injection levels after several weeks. Additionally, Fe(II)-oxidizing, nitrate-reducing microbial enrichment cultures were obtained from aquifer sediments. Growth experiments with the cultures sequentially produced nitrite and nitrous oxide from nitrate while simultaneously oxidizing Fe(II). Field and culture results suggest that nitrogen oxide reduction and Fe(II) oxidation in the aquifer are a complex interaction of coupled biotic and abiotic reactions. Overall, the results of this study demonstrate that anoxic nitrate-dependent iron oxidation can occur in groundwater; that it could control iron speciation; and that the process can impact the mobility of other chemical species (e.g., phosphate and arsenic) not directly involved in the oxidation–reduction reaction.

Anoxic nitrate reduction coupled with iron oxidation and attenuation of dissolved arsenic and phosphate in a sand and gravel aquifer

NASA Astrophysics Data System (ADS)

Smith, Richard L.; Kent, Douglas B.; Repert, Deborah A.; Böhlke, J. K.

2017-01-01

Nitrate has become an increasingly abundant potential electron acceptor for Fe(II) oxidation in groundwater, but this redox couple has not been well characterized within aquifer settings. To investigate this reaction and some of its implications for redox-sensitive groundwater contaminants, we conducted an in situ field study in a wastewater-contaminated aquifer on Cape Cod. Long-term (15 year) geochemical monitoring within the contaminant plume indicated interacting zones with variable nitrate-, Fe(II)-, phosphate-, As(V)-, and As(III)-containing groundwater. Nitrate and phosphate were derived predominantly from wastewater disposal, whereas Fe(II), As(III), and As(V) were mobilized from the aquifer sediments. Multiple natural gradient, anoxic tracer tests were conducted in which nitrate and bromide were injected into nitrate-free, Fe(II)-containing groundwater. Prior to injection, aqueous Fe(II) concentrations were approximately 175 μM, but sorbed Fe(II) accounted for greater than 90% of the total reactive Fe(II) in the aquifer. Nitrate reduction was stimulated within 1 m of transport for 100 μM and 1000 μM nitrate additions, initially producing stoichiometric quantities of nitrous oxide (>300 μM N). In subsequent injections at the same site, nitrate was reduced even more rapidly and produced less nitrous oxide, especially over longer transport distances. Fe(II) and nitrate concentrations decreased together and were accompanied by Fe(III) oxyhydroxide precipitation and decreases in dissolved phosphate, As(III), and As(V) concentrations. Nitrate N and O isotope fractionation effects during nitrate reduction were approximately equal (ε15N/ε18O = 1.11) and were similar to those reported for laboratory studies of biological nitrate reduction, including denitrification, but unlike some reported effects on nitrate by denitrification in aquifers. All constituents affected by the in situ tracer experiments returned to pre-injection levels after several weeks. Additionally, Fe(II)-oxidizing, nitrate-reducing microbial enrichment cultures were obtained from aquifer sediments. Growth experiments with the cultures sequentially produced nitrite and nitrous oxide from nitrate while simultaneously oxidizing Fe(II). Field and culture results suggest that nitrogen oxide reduction and Fe(II) oxidation in the aquifer are a complex interaction of coupled biotic and abiotic reactions. Overall, the results of this study demonstrate that anoxic nitrate-dependent iron oxidation can occur in groundwater; that it could control iron speciation; and that the process can impact the mobility of other chemical species (e.g., phosphate and arsenic) not directly involved in the oxidation-reduction reaction.

Uranium chloride extraction of transuranium elements from LWR fuel

DOEpatents

Miller, W.E.; Ackerman, J.P.; Battles, J.E.; Johnson, T.R.; Pierce, R.D.

1992-08-25

A process of separating transuranium actinide values from uranium values present in spent nuclear oxide fuels containing rare earth and noble metal fission products as well as other fission products is disclosed. The oxide fuel is reduced with Ca metal in the presence of Ca chloride and a U-Fe alloy which is liquid at about 800 C to dissolve uranium metal and the noble metal fission product metals and transuranium actinide metals and rare earth fission product metals leaving Ca chloride having CaO and fission products of alkali metals and the alkali earth metals and iodine dissolved therein. The Ca chloride and CaO and the fission products contained therein are separated from the U-Fe alloy and the metal values dissolved therein. The U-Fe alloy having dissolved therein reduced metals from the spent nuclear fuel is contacted with a mixture of one or more alkali metal or alkaline earth metal halides selected from the class consisting of alkali metal or alkaline earth metal and Fe or U halide or a combination thereof to transfer transuranium actinide metals and rare earth metals to the halide salt leaving the uranium and some noble metal fission products in the U-Fe alloy and thereafter separating the halide salt and the transuranium metals dissolved therein from the U-Fe alloy and the metals dissolved therein. 1 figure.

Uranium chloride extraction of transuranium elements from LWR fuel

DOEpatents

Miller, William E.; Ackerman, John P.; Battles, James E.; Johnson, Terry R.; Pierce, R. Dean

1992-01-01

A process of separating transuranium actinide values from uranium values present in spent nuclear oxide fuels containing rare earth and noble metal fission products as well as other fission products is disclosed. The oxide fuel is reduced with Ca metal in the presence of Ca chloride and a U-Fe alloy which is liquid at about 800.degree. C. to dissolve uranium metal and the noble metal fission product metals and transuranium actinide metals and rare earth fission product metals leaving Ca chloride having CaO and fission products of alkali metals and the alkali earth metals and iodine dissolved therein. The Ca chloride and CaO and the fission products contained therein are separated from the U-Fe alloy and the metal values dissolved therein. The U-Fe alloy having dissolved therein reduced metals from the spent nuclear fuel is contacted with a mixture of one or more alkali metal or alkaline earth metal halides selected from the class consisting of alkali metal or alkaline earth metal and Fe or U halide or a combination thereof to transfer transuranium actinide metals and rare earth metals to the halide salt leaving the uranium and some noble metal fission products in the U-Fe alloy and thereafter separating the halide salt and the transuranium metals dissolved therein from the U-Fe alloy and the metals dissolved therein.

Release of dissolved phosphorus from riparian wetlands: Evidence for complex interactions among hydroclimate variability, topography and soil properties.

PubMed

Gu, Sen; Gruau, Gérard; Dupas, Rémi; Rumpel, Cornélia; Crème, Alexandra; Fovet, Ophélie; Gascuel-Odoux, Chantal; Jeanneau, Laurent; Humbert, Guillaume; Petitjean, Patrice

2017-11-15

In agricultural landscapes, establishment of vegetated buffer zones in riparian wetlands (RWs) is promoted to decrease phosphorus (P) emissions because RWs can trap particulate P from upslope fields. However, long-term accumulation of P risks the release of dissolved P, since the unstable hydrological conditions in these zones may mobilize accumulated particulate P by transforming it into a mobile dissolved P species. This study evaluates how hydroclimate variability, topography and soil properties interact and influence this mobilization, using a three-year dataset of molybdate-reactive dissolved P (MRDP) and total dissolved P (TDP) concentrations in soil water from two RWs located in an agricultural catchment in western France (Kervidy-Naizin), along with stream P concentrations. Two main drivers of seasonal dissolved P release were identified: i) soil rewetting during water-table rise after dry periods and ii) reductive dissolution of soil Fe (hydr)oxides during prolonged water saturation periods. These mechanisms were shown to vary greatly in space (according to topography) and time (according to intra- and interannual hydroclimate variability). The concentration and speciation of the released dissolved P also varied spatially depending on soil chemistry and local topography. Comparison of sites revealed a similar correlation between soil P speciation (percentage of organic P ranging from 35-70%) and the concentration and speciation of the released P (MRDP from <0.10 to 0.40mgl -1 ; percentage of MRDP in TDP from 25-70%). These differences propagated to stream water, suggesting that the two RWs investigated were the main sources of dissolved P to streams. RWs can be critical areas due to their ability to biogeochemically transform the accumulated P in these zones into highly mobile and highly bioavailable dissolved P forms. Hydroclimate variability, local topography and soil chemistry must be considered to decrease the risk of remobilizing legacy soil P when establishing riparian buffer zones in agricultural landscapes. Copyright © 2017 Elsevier B.V. All rights reserved.

Variation of iron redox kinetics and its relation with molecular composition of standard humic substances at circumneutral pH.

PubMed

Lee, Ying Ping; Fujii, Manabu; Kikuchi, Tetsuro; Terao, Koumei; Yoshimura, Chihiro

2017-01-01

Oxidation and reduction kinetics of iron (Fe) and proportion of steady-state Fe(II) concentration relative to total dissolved Fe (steady-state Fe(II) fraction) were investigated in the presence of various types of standard humic substances (HS) with particular emphasis on the photochemical and thermal reduction of Fe(III) and oxidation of Fe(II) by dissolved oxygen (O2) and hydrogen peroxide (H2O2) at circumneutral pH (pH 7-8). Rates of Fe(III) reduction were spectrophotometrically determined by a ferrozine method under the simulated sunlight and dark conditions, whereas rates of Fe(II) oxidation were examined in air-saturated solution using luminol chemiluminescence technique. The reduction and oxidation rate constants were determined to substantially vary depending on the type of HS. For example, the first-order rate constants varied by up to 10-fold for photochemical reduction and 7-fold for thermal reduction. The degree of variation in Fe(II) oxidation was larger for the H2O2-mediated reaction compared to the O2-mediated reaction (e.g., 15- and 3-fold changes for the former and latter reactions, respectively, at pH 8). The steady-state Fe(II) fraction under the simulated sunlight indicated that the Fe(II) fraction varies by up to 12-fold. The correlation analysis indicated that variation of Fe(II) oxidation is significantly associated with aliphatic content of HS, suggesting that Fe(II) complexation by aliphatic components accelerates Fe(II) oxidation. The reduction rate constant and steady-state Fe(II) fractions in the presence of sunlight had relatively strong positive relations with free radical content of HS, possibly due to the reductive property of radical semiquinone in HS. Overall, the findings in this study indicated that the Fe reduction and oxidation kinetics and resultant Fe(II) formation are substantially influenced by chemical properties of HS.

Year-round record of dissolved and particulate metals in surface snow at Dome Concordia (East Antarctica).

PubMed

Grotti, Marco; Soggia, Francesco; Ardini, Francisco; Magi, Emanuele; Becagli, Silvia; Traversi, Rita; Udisti, Roberto

2015-11-01

From January to December 2010, surface snow samples were collected with monthly resolution at the Concordia station (75°06'S, 123°20'E), on the Antarctic plateau, and analysed for major and trace elements in both dissolved and particulate (i.e. insoluble particles, >0.45 μm) phase. Additional surface snow samples were collected with daily resolution, for the determination of sea-salt sodium and not-sea-salt calcium, in order to support the discussion on the seasonal variations of trace elements. Concentrations of alkaline and alkaline-earth elements were higher in winter (April-October) than in summer (November-March) by a factor of 1.2-3.3, in agreement with the higher concentration of sea-salt atmospheric particles reaching the Antarctic plateau during the winter. Similarly, trace elements were generally higher in winter by a factor of 1.2-1.5, whereas Al and Fe did not show any significant seasonal trend. Partitioning between dissolved and particulate phases did not change with the sampling period, but it depended only on the element: alkaline and alkaline-earth elements, as well as Co, Cu, Mn, Pb and Zn were for the most part (>80%) in the dissolved phase, whereas Al and Fe were mainly associated with the particulate phase (>80%) and Cd, Cr, V were nearly equally distributed between the phases. Finally, the estimated marine and crustal enrichment factors indicated that Cd, Cr, Cu, Pb and Zn have a dominant anthropogenic origin, with a possible contribution from the Concordia station activities. Copyright © 2014 Elsevier Ltd. All rights reserved.

Fate of colloids during estuarine mixing in the Arctic

NASA Astrophysics Data System (ADS)

Pokrovsky, O. S.; Shirokova, L. S.; Viers, J.; Gordeev, V. V.; Shevchenko, V. P.; Chupakov, A. V.; Vorobieva, T. Y.; Candaudap, F.; Causserand, C.; Lanzanova, A.; Zouiten, C.

2014-02-01

The estuarine behavior of organic carbon (OC) and trace elements (TE) was studied for the largest European sub-Arctic river, which is the Severnaya Dvina; this river has a deltaic estuary covered in ice during several hydrological seasons: summer (July 2010, 2012) and winter (March 2009) baseflow, and the November-December 2011 ice-free period. Colloidal forms of OC and TE were assessed for three pore size cutoffs (1, 10, and 50 kDa) using an in situ dialysis procedure. Conventionally dissolved (< 0.22 μm) fractions demonstrated clear conservative behavior for Li, B, Na, Mg, K, Ca, Sr, Mo, Rb, Cs, and U during the mixing of freshwater with the White Sea; a significant (up to a factor of 10) concentration increase occurs with increases in salinity. Si and OC also displayed conservative behavior but with a pronounced decrease in concentration seawards. Rather conservative behavior, but with much smaller changes in concentration (variation within ±30%) over a full range of salinities, was observed for Ti, Ni, Cr, As, Co, Cu, Ga, Y, and heavy REE. Strong non-conservative behavior with coagulation/removal at low salinities (< 5‰) was exhibited by Fe, Al, Zr, Hf, and light REE. Finally, certain divalent metals exhibited non-conservative behavior with a concentration gain at low (~ 2-5‰, Ba, Mn) or intermediate (~ 10-15‰, Ba, Zn, Pb, Cd) salinities, which is most likely linked to TE desorption from suspended matter or sediment outflux. The most important result of this study is the elucidation of the behavior of the "truly" dissolved low molecular weight LMW< 1 kDa fraction containing Fe, OC, and a number of insoluble elements. The concentration of the LMW fraction either remains constant or increases its relative contribution to the overall dissolved (< 0.22 μm) pool as the salinity increases. Similarly, the relative proportion of colloidal (1 kDa-0.22 μm) pool for the OC and insoluble TE bound to ferric colloids systematically decreased seaward, with the largest decrease occurring at low (< 5‰) salinities. Overall, the observed decrease in the colloidal fraction may be related to the coagulation of organo-ferric colloids at the beginning of the mixing zone and therefore the replacement of the HMW1 kDa-0.22 μm portion by the LMW< 1 kDa fraction. These patterns are highly reproducible across different sampling seasons, suggesting significant enrichment of the mixing zone by the most labile (and potentially bioavailable) fraction of the OC, Fe and insoluble TE. The size fractionation of the colloidal material during estuarine mixing reflects a number of inorganic and biological processes, the relative contribution of which to element speciation varies depending on the hydrological stage and time of year. In particular, LMW< 1 kDa ligand production in the surface horizons of the mixing zone may be linked to heterotrophic mineralization of allochthonous DOM and/or photodestruction. Given the relatively low concentration of particulate versus dissolved load of most trace elements, desorption from the river suspended material was less pronounced than in other rivers in the world. As a result, the majority of dissolved components exhibited either conservative (OC and related elements such as divalent metals) or non-conservative, coagulation-controlled (Fe, Al, and insoluble TE associated with organo-ferric colloids) behavior. The climate warming at high latitudes is likely to intensify the production of LMW< 1 kDa organic ligands and the associated TE; therefore, the delivery of potentially bioavailable trace metal micronutrients from the land to the ocean may increase.

Porewater dynamics of silver, lead and copper in coastal sediments and implications for benthic metal fluxes

USGS Publications Warehouse

Kalnejais, Linda H.; Martin, W. R.; Bothner, Michael H.

2015-01-01

To determine the conditions that lead to a diffusive release of dissolved metals from coastal sediments, porewater profiles of Ag, Cu, and Pb have been collected over seven years at two contrasting coastal sites in Massachusetts, USA. The Hingham Bay (HB) site is a contaminated location in Boston Harbor, while the Massachusetts Bay (MB) site is 11 km offshore and less impacted. At both sites, the biogeochemical cycles include scavenging by Fe-oxyhydroxides and release of dissolved metals when Fe-oxyhydroxides are reduced. Important differences in the metal cycles at the two sites, however, result from different redox conditions. Porewater sulfide and seasonal variation in redox zone depth is observed at HB, but not at MB. In summer, as the conditions become more reducing at HB, trace metals are precipitated as sulfides and are no longer associated with Fe-oxyhydroxides. Sulfide precipitation close to the sediment–water interface limits the trace metal flux in summer and autumn at HB, while in winter, oxidation of the sulfide phases drives high benthic fluxes of Cu and Ag, as oxic conditions return. The annual diffusive flux of Cu at HB is found to be significant and contributes to the higher than expected water column Cu concentrations observed in Boston Harbor. At MB, due to the lower sulfide concentrations, the association of trace metals with Fe-oxyhydroxides occurs throughout the year, leading to more stable fluxes. A surface enrichment of solid phase trace metals was found at MB and is attributed to the persistent scavenging by Fe-oxyhydroxides. This process is important, particularly at sites that are less reducing, because it maintains elevated metal concentrations at the surface despite the effects of bioturbation and sediment accumulation, and because it may increase the persistence of metal contamination in surface sediments.

Role of hydrous iron oxide formation in attenuation and diel cycling of dissolved trace metals in a stream affected by acid rock drainage

USGS Publications Warehouse

Parker, S.R.; Gammons, C.H.; Jones, Clain A.; Nimick, D.A.

2007-01-01

Mining-impacted streams have been shown to undergo diel (24-h) fluctuations in concentrations of major and trace elements. Fisher Creek in south-central Montana, USA receives acid rock drainage (ARD) from natural and mining-related sources. A previous diel field study found substantial changes in dissolved metal concentrations at three sites with differing pH regimes during a 24-h period in August 2002. The current work discusses follow-up field sampling of Fisher Creek as well as field and laboratory experiments that examine in greater detail the underlying processes involved in the observed diel concentration changes. The field experiments employed in-stream chambers that were either transparent or opaque to light, filled with stream water and sediment (cobbles coated with hydrous Fe and Al oxides), and placed in the stream to maintain the same temperature. Three sets of laboratory experiments were performed: (1) equilibration of a Cu(II) and Zn(II) containing solution with Fisher Creek stream sediment at pH 6.9 and different temperatures; (2) titration of Fisher Creek water from pH 3.1 to 7 under four different isothermal conditions; and (3) analysis of the effects of temperature on the interaction of an Fe(II) containing solution with Fisher Creek stream sediment under non-oxidizing conditions. Results of these studies are consistent with a model in which Cu, Fe(II), and to a lesser extent Zn, are adsorbed or co-precipitated with hydrous Fe and Al oxides as the pH of Fisher Creek increases from 5.3 to 7.0. The extent of metal attenuation is strongly temperature-dependent, being more pronounced in warm vs. cold water. Furthermore, the sorption/co-precipitation process is shown to be irreversible; once the Cu, Zn, and Fe(II) are removed from solution in warm water, a decrease in temperature does not release the metals back to the water column. ?? 2006 Springer Science+Business Media B.V.

Impact of natural organic matter on arsenic removal by modified granular natural siderite: Evidence of ternary complex formation by HPSEC-UV-ICP-MS.

PubMed

Li, Fulan; Guo, Huaming; Zhou, Xiaoqian; Zhao, Kai; Shen, Jiaxing; Liu, Fei; Wei, Chao

2017-02-01

High arsenic (As) groundwater usually has high concentrations of natural organic matter (NOM). Effects of NOM on arsenic adsorption were investigated to evaluate the efficiency of modified granular natural siderite (MGNS) as an adsorbent for groundwater arsenic remediation. Humic and fulvic acids (HA/FA) were selected as model NOM compounds. In batch tests, HA or FA was either first adsorbed onto the MGNS, or applied together with dissolved arsenic to investigate effects of both adsorbed and dissolved NOM on arsenic removal. The kinetic data showed no significant effects of both adsorbed and dissolved HA/FA on As(III) adsorption. However, As(V) removal was inhibited, whereby the adsorbed NOM compounds had greater inhibitory effect. The inhibitory effect on As(V) removal increased with increasing NOM concentrations. FA exhibited higher inhibitory effect than HA at the same concentration. Steric Exclusion Chromatography-HPLC (SEC-HPLC), and High-Performance Size Exclusion Chromatography-UV-Inductively Coupled Plasma Mass Spectrometry (HPSEC-UV-ICP-MS) revealed that As(V) removal was mostly achieved by the oxyanion adsorption and adversely affected by dissolved FA via competitive adsorption for surface sites. In addition to oxyanion adsorption, removal of As(V) was related to scavenging of ternary HA-As-Fe complexes, which led to the less inhibitory effect of dissolved HA on As(V) removal than dissolved FA via competitive adsorption. Copyright © 2016 Elsevier Ltd. All rights reserved.

Catalytic effect of light illumination on bioleaching of chalcopyrite.

PubMed

Zhou, Shuang; Gan, Min; Zhu, Jianyu; Li, Qian; Jie, Shiqi; Yang, Baojun; Liu, Xueduan

2015-04-01

The influence of visible light exposure on chalcopyrite bioleaching was investigated using Acidithiobacillus ferrooxidans. The results indicated, in both shake-flasks and aerated reactors with 8500-lux light, the dissolved Cu was 91.80% and 23.71% higher, respectively, than that in the controls without light. The catalytic effect was found to increase bioleaching to a certain limit, then plateaued as the initial chalcopyrite concentration increased from 2% to 4.5%. Thus a balanced mineral concentration is highly amenable to bioleaching via offering increased available active sites for light adsorption while eschewing mineral aggregation and screening effects. Using semiconducting chalcopyrite, the light facilitated the reduction of Fe(3+) to Fe(2+) as metabolic substrates for A.ferrooxidans, leading to better biomass, lower pH and redox potential, which are conducive to chalcopyrite leaching. The light exposure on iron redox cycling was further confirmed by chemical leaching tests using Fe(3+), which exhibited higher Fe(2+) levels in the light-induced system. Copyright © 2015 Elsevier Ltd. All rights reserved.

Localized sulfate-reducing zones in a coastal plain aquifer

USGS Publications Warehouse

Brown, C.J.; Coates, J.D.; Schoonen, M.A.A.

1999-01-01

High concentrations of dissolved iron in ground water of coastal plain or alluvial aquifers contribute to the biofouling of public supply wells for which treatment and remediation is costly. Many of these aquifers, however, contain zones in which microbial sulfate reduction and the associated precipitation of iron-sulfide minerals decreases iron mobility. The principal water-bearing aquifer (Magothy Aquifer of Cretaceous age) in Suffolk County, New York, contains localized sulfate-reducing zones in and near lignite deposits, which generally are associated with clay lenses. Microbial analyses of core samples amended with [14C]-acetate indicate that microbial sulfate reduction is the predominant terminal-electron-accepting process (TEAP) in poorly permeable, lignite-rich sediments at shallow depths and near the ground water divide. The sulfate-reducing zones are characterized by abundant lignite and iron-sulfide minerals, low concentrations of Fe(III) oxyhydroxides, and by proximity to clay lenses that contain pore water with relatively high concentrations of sulfate and dissolved organic carbon. The low permeability of these zones and, hence, the long residence time of ground water within them, permit the preservation and (or) allow the formation of iron-sulfide minerals, including pyrite and marcasite. Both sulfate-reducing bacteria (SRB) and iron-reducing bacteria (IRB) are present beneath and beyond the shallow sulfate-reducing zones. A unique Fe(III)-reducing organism, MD-612, was found in core sediments from a depth of 187 m near the southern shore of Long Island. The distribution of poorly permeable, lignite-rich, sulfate-reducing zones with decreased iron concentration is varied within the principal aquifer and accounts for the observed distribution of dissolved sulfate, iron, and iron sulfides in the aquifer. Locating such zones for the placement of production wells would be difficult, however, because these zones are of limited aerial extent.

Characteristics of Fe powders prepared by spray pyrolysis from a spray solution with ethylene glycol as the source material of heat pellet

NASA Astrophysics Data System (ADS)

Koo, H. Y.; Kim, J. H.; Hong, S. K.; Ko, Y. N.; Jang, H. C.; Jung, D. S.; Han, J. M.; Hong, Y. J.; Kang, Y. C.; Kang, S. H.; Cho, S. B.

2012-06-01

Fe powders as the heat pellet material for thermal batteries are prepared from iron oxide powders obtained by spray pyrolysis from a spray solution of iron nitrate with ethylene glycol. The iron oxide powders with hollow and thin wall structure produce Fe powders with elongated structure and fine primary particle size at a low reducing temperature of 615 °C. The mean size of the primary Fe powders with elongated structure decreases with increasing concentration of ethylene glycol dissolved into the spray solution. The heat pellets prepared from the fine-size Fe powders with elongated structure have good ignition sensitivities below 1 watt. The heat pellets formed from the Fe powders obtained from the spray solution with 0.5 M EG have an extremely high burn rate of 26 cms-1.

Iron-rich colloids as carriers of phosphorus in streams: A field-flow fractionation study.

PubMed

Baken, Stijn; Regelink, Inge C; Comans, Rob N J; Smolders, Erik; Koopmans, Gerwin F

2016-08-01

Colloidal phosphorus (P) may represent an important fraction of the P in natural waters, but these colloids remain poorly characterized. In this work, we demonstrate the applicability of asymmetric flow field-flow fractionation (AF4) coupled to high resolution ICP-MS for the characterization of low concentrations of P-bearing colloids. Colloids from five streams draining catchments with contrasting properties were characterized by AF4-ICP-MS and by membrane filtration. All streams contain free humic substances (2-3 nm) and Fe-bearing colloids (3-1200 nm). Two soft water streams contain primary Fe oxyhydroxide-humic nanoparticles (3-6 nm) and aggregates thereof (up to 150 nm). In contrast, three harder water streams contain larger aggregates (40-1200 nm) which consist of diverse associations between Fe oxyhydroxides, humic substances, clay minerals, and possibly ferric phosphate minerals. Despite the diversity of colloids encountered in these contrasting streams, P is in most of the samples predominantly associated with Fe-bearing colloids (mostly Fe oxyhydroxides) at molar P:Fe ratios between 0.02 and 1.5. The molar P:Fe ratio of the waters explains the partitioning of P between colloids and truly dissolved species. Waters with a high P:Fe ratio predominantly contain truly dissolved species because the Fe-rich colloids are saturated with P, whereas waters with a low P:Fe ratio mostly contain colloidal P species. Overall, AF4-ICP-MS is a suitable technique to characterize the diverse P-binding colloids in natural waters. Such colloids may increase the mobility or decrease the bioavailability of P, and they therefore need to be considered when addressing the transport and environmental effects of P in catchments. Copyright © 2016 Elsevier Ltd. All rights reserved.

Dissolved and particulate Barium in the Ganga (Hooghly) River estuary, India: Solute-particle interactions and the enhanced dissolved flux to the oceans

NASA Astrophysics Data System (ADS)

Samanta, Saumik; Dalai, Tarun K.

2016-12-01

In this study, the sources and the cycling of Ba have been evaluated in the Ganga (Hooghly) River estuary using the composition of the suspended sediments and the water samples collected during six seasons of contrasting water discharge over two years (2012 and 2013). In addition, the data on the samples of groundwater from areas adjacent to the estuary, and the industrial effluent water and urban wastewater draining into the estuary are presented. Selective extraction experiments were also performed on the suspended particulate matter of two seasons to assess the distribution of exchangeable concentrations of major ions and Ba. In the mixing zone, the variation patterns of the dissolved Ba concentrations show mid-salinity maxima and are similar to the patterns of variation of the particulate Mg/Al and Mg/Fe, suggesting that the production of dissolved Ba is linked to the adsorption of major ions on to the clay minerals and Fe-Mn oxyhydroxides in the particulate matter. The inference of coupled adsorption-desorption processes is supported by the observations that the particulate Ba/Mg and Ba/K ratios exhibit significant to strong negative correlations with the concentrations of Al, Fe and Mn. The observations of mid-salinity maxima for the concentrations of exchangeable Mg and K, and of the exchangeable Ba concentrations that decrease with salinity provide strong evidence that the solute-particle interactions is the major driver in regulating the dissolved Ba distributions in the estuary. The estimates of the quantity of desorbed Ba based on three different approaches suggest that desorption is sufficient to account for the calculated excess Ba (Baxs) concentrations. The contribution of Ba to the dissolved load via dissolution of the particulate carbonate phases is minor, up to 3% of the maximum Baxs concentrations. The estimates of anthropogenic contributions are insignificant, and account for ⩽2% of maximum Baxs in the estuary. Groundwater contributions are less significant and account for up to 5% of the annual Ba flux from the Hooghly estuary. The estimates of Ba flux show that annually (1.5-1.9) × 107 moles of Ba is transported by the Hooghly River. About (3.6-4.3) × 107 moles of Ba is generated annually in the estuary through desorption. Added together, the desorbed and riverine Ba fluxes generate a total Ba flux of (5.1-6.2) × 107 moles per year. Thus, the solute-particle interactions enhance the riverine Ba flux by >300%. A compilation of the available data shows that the enhancement of the riverine Ba flux and the fractions of desorbed Ba flux scale with (particulate matter flux/water flux) ratio in several estuaries of the world, suggesting that the process of solute-particle interactions is a major driver for the estuarine production of Ba on a global scale. Among the rivers considered in this study, the estuaries of the Hooghly River and the Ganges-Brahmaputra rivers, characterized by very high (sediment flux/water flux) ratio, depict the highest increase in the riverine Ba flux. This unique feature of the Ganga River system is inferred to be resulting from the collective impact of the tectonic activity and the monsoonal rainfall in the catchment areas.

Trace metals partitioning between particulate and dissolved phases along a tropical mangrove estuary (Can Gio, Vietnam).

PubMed

Thanh-Nho, Nguyen; Strady, Emilie; Nhu-Trang, Tran-Thi; David, Frank; Marchand, Cyril

2018-04-01

Mangroves can be considered as biogeochemical reactors along (sub)tropical coastlines, acting both as sinks or sources for trace metals depending on environmental factors. In this study, we characterized the role of a mangrove estuary, developing downstream a densely populated megacity (Ho Chi Minh City, Vietnam), on the fate and partitioning of trace metals. Surface water and suspended particulate matter were collected at four sites along the estuarine salinity gradient during 24 h cycling in dry and rainy seasons. Salinity, pH, DO, TSS, POC, DOC, dissolved and particulate Fe, Mn, Cr, As, Cu, Ni, Co and Pb were measured. TSS was the main trace metals carrier during their transit in the estuary. However, TSS variations did not explain the whole variability of metals distribution. Mn, Cr and As were highly reactive metals while the other metals (Fe, Ni, Cu, Co and Pb) presented stable log K D values along the estuary. Organic matter dynamic appeared to play a key role in metals fractioning. Its decomposition during water transit in the estuary induced metal desorption, especially for Cr and As. Conversely, dissolved Mn concentrations decreased along the estuary, which was suggested to result from Mn oxidative precipitation onto solid phase due to oxidation and pH changes. Extra sources as pore-water release, runoff from adjacent soils, or aquaculture effluents were suggested to be involved in trace metal dynamic in this estuary. In addition, the monsoon increased metal loads, notably dissolved and particulate Fe, Cr, Ni and Pb. Copyright © 2018 Elsevier Ltd. All rights reserved.

The effects of iron(II) on the kinetics of arsenic oxidation and sorption on manganese oxides.

PubMed

Wu, Yun; Li, Wei; Sparks, Donald L

2015-11-01

In this study, As(III) oxidation kinetics by a poorly-crystalline phyllomanganate (δ-MnO2) in the presence and absence of dissolved Fe(II) was investigated using stirred-flow and batch experiments. Chemically synthetic δ-MnO2 was reacted with four influent solutions, containing the same As(III) concentration but different Fe(II) concentrations, at pH 6. The results show an initial rapid As(III) oxidation by δ-MnO2, which is followed by an appreciably slow reaction after 8h. In the presence of Fe(II), As(III) oxidation is inhibited due to the competitive oxidation of Fe(II) as well as the formation of Fe(III)-(hydr)oxides on the δ-MnO2 surface. However, the sorption of As(III), As(V) and Mn(II) are increased, for the newly formed Fe(III)-(hydr)oxides provide additional sorption sites. This study suggests that the competitive oxidation of Fe(II) and consequently the precipitation of Fe(III) compounds on the δ-MnO2 surface play an important role in As(III) oxidation and As sequestration. Understanding these processes would be helpful in developing in situ strategies for remediation of As-contaminated waters and soils. Copyright © 2015 Elsevier Inc. All rights reserved.

Kinetics of homogeneous and surface-catalyzed mercury(II) reduction by iron(II)

USGS Publications Warehouse

Amirbahman, Aria; Kent, Douglas B.; Curtis, Gary P.; Marvin-DiPasquale, Mark C.

2013-01-01

Production of elemental mercury, Hg(0), via Hg(II) reduction is an important pathway that should be considered when studying Hg fate in environment. We conducted a kinetic study of abiotic homogeneous and surface-catalyzed Hg(0) production by Fe(II) under dark anoxic conditions. Hg(0) production rate, from initial 50 pM Hg(II) concentration, increased with increasing pH (5.5–8.1) and aqueous Fe(II) concentration (0.1–1 mM). The homogeneous rate was best described by the expression, rhom = khom [FeOH+] [Hg(OH)2]; khom = 7.19 × 10+3 L (mol min)−1. Compared to the homogeneous case, goethite (α-FeOOH) and hematite (α-Fe2O3) increased and γ-alumina (γ-Al2O3) decreased the Hg(0) production rate. Heterogeneous Hg(0) production rates were well described by a model incorporating equilibrium Fe(II) adsorption, rate-limited Hg(II) reduction by dissolved and adsorbed Fe(II), and rate-limited Hg(II) adsorption. Equilibrium Fe(II) adsorption was described using a surface complexation model calibrated with previously published experimental data. The Hg(0) production rate was well described by the expression rhet = khet [>SOFe(II)] [Hg(OH)2], where >SOFe(II) is the total adsorbed Fe(II) concentration; khet values were 5.36 × 10+3, 4.69 × 10+3, and 1.08 × 10+2 L (mol min)−1 for hematite, goethite, and γ-alumina, respectively. Hg(0) production coupled to reduction by Fe(II) may be an important process to consider in ecosystem Hg studies.

Evaluation of the capability of low-impact development practices for the removal of heavy metal from urban stormwater runoff.

PubMed

Maniquiz-Redillas, Marla C; Kim, Lee-Hyung

2016-09-01

Low-impact development (LID) and green infrastructure (GI) have recently become well-known methods to capture, collect, retain, and remove pollutants in stormwater runoff. The research was conducted to assess the efficiency of LID/GI systems applied in removing the particulate and dissolved heavy metals (Zn, Pb, Cu, Ni, Cr, Cd, and Fe) from urban stormwater runoff. A total of 82 storm events were monitored over a four-year period (2010-2014) on six LID/GI systems including infiltration trenches, tree box filter, rain garden, and hybrid constructed wetlands employed for the management of road, parking lot, and roof runoff. It was observed that the heavy metal concentration increased proportionally with the total suspended solids concentration. Among the heavy metal constituents, Fe appeared to be highly particulate-bound and was the easiest to remove followed by Zn and Pb; while metals such as Cr, Ni, Cu, and Cd were mostly dissolved and more difficult to remove. The mass fraction ratios of metal constituents at the effluent were increased relative to the influent. All the systems performed well in the removal of particulate-bound metals and were more efficient for larger storms greater than 15 mm wherein more particulate-bound metals were generated compared to smaller storms less than 5 mm that produced more dissolved metals. The efficiency of the systems in removing the particulate-bound metals was restricted during high average/peak flows; that is, high-intensity storms events and when heavy metals have low concentration levels.

Sources of variability in livestock water quality over 5 years in the Northern Great Plains

USDA-ARS?s Scientific Manuscript database

Mineral content of livestock water grazing rangelands can be a source of minerals affecting health and drinkability. To estimate yearly variation in water mineral concentrations, 11 indicators of quality were measured (Ca, Cl, Fe, Fl, Mg, Mn, Na, NO3-N, pH, SO4, total dissolved solids (TDS) and temp...

Nitrate removal by Fe0/Pd/Cu nano-composite in groundwater.

PubMed

Liu, Hongyuan; Guo, Min; Zhang, Yan

2014-01-01

Nitrate pollution in groundwater shows a great threat to the safety of drinking water. Chemical reduction by zero-valent iron is being considered as a promising technique for nitrate removal from contaminated groundwater. In this paper, Fe0/Pd/Cu nano-composites were prepared by the liquid-phase reduction method, and batch experiments of nitrate reduction by the prepared Fe0/Pd/Cu nano-composites under various operating conditions were carried out. It has been found that nano-Fe0/Pd/Cu composites processed dual functions: catalytic reduction and chemical reduction. The introduction of Pd and Cu not only improved nitrate removal rate, but also reduced the generation of ammonia. Nitrate removal rate was affected by the amount of Fe0/Pd/Cu, initial nitrate concentration, solution pH, dissolved oxygen (DO), reaction temperature, the presence of anions, and organic pollutant. Moreover, nitrate reduction by Fe0/Pd/Cu composites followed the pseudo-first-order reaction kinetics. The removal rate of nitrate and total nitrogen were about 85% and 40.8%, respectively, under the reaction condition of Fe-6.0%Pd-3.0%Cu amount of 0.25 g/L, pH value of 7.1, DO of 0.42 mg/L, and initial nitrate concentration of 100 mg/L. Compared with the previous studies with Fe0 alone or Fe-Cu, nano-Fe-6%Pd-3%Cu composites showed a better selectivity to N2.

Characterizing the production and retention of dissolved iron as Fe(II) across a natural gradient in chlorophyll concentrations in the Southern Drake Passage - Final Technical Report

DOE Office of Scientific and Technical Information (OSTI.GOV)

Katherine Barbeau

2007-04-10

Recent mesoscale iron fertilization studies in the Southern Ocean (e.g. SOIREE, EisenEx, SOFeX) have demonstrated the importance of iron as a limiting factor for phytoplankton growth in these high nutrient, low-chlorophyll (HNLC) waters. Results of these experiments have demonstrated that factors which influence the biological availability of the iron supplied to phytoplankton are crucial in bloom development, longevity, and generation of carbon export flux. These findings have important implications for the future development of iron fertilization protocols to enhance carbon sequestration in high-latitude oceans. In particular, processes which lead to the mobilization and retention of iron in dissolved form inmore » the upper ocean are important in promoting continued biological availability of iron. Such processes can include photochemical redox cycling, which leads to the formation of soluble reduced iron, Fe(II), within iron-enriched waters. Creation of effective fertilization schemes will thus require more information about Fe(II) photoproduction in Southern Ocean waters as a means to retain new iron within the euphotic zone. To contribute to our knowledge base in this area, this project was funded by DOE with a goal of characterizing the production and retention of dissolved Fe as Fe(II) in an area of the southern Drake Passage near the Shackleton Transverse Ridge, a region with a strong recurrent chlorophyll gradient which is believed to be a site of natural iron enrichment in the Southern Ocean. This area was the focus of a multidisciplinary NSF/OPP-funded investigation in February 2004 (OPP02-30443, lead PI Greg Mitchell, SIO/UCSD) to determine the influence of mesoscale circulation and iron transport with regard to the observed patterns in sea surface chlorophyll in the region near the Shackleton Transverse Ridge. A number of parameters were assessed across this gradient in order to reveal interactions between plankton community structure and iron distributions. As a co-PI in the NSF/OPP-funded project, I was responsible for iron addition incubation and radiotracer experiments, and analysis of iron chemistry, including iron-organic speciation. This final technical report describes the results of my DOE funded project to analyse reduced iron species using an FeLume flow injection analysis chemiluminescence system as an extension of my work on the NSF/OPP project. On the cruise in 2004, spatial and temporal gradients in Fe(II) were determined, and on-board incubations were conducted to study Fe(II) lifetime and production. Following the cruise a further series of experiments was conducted in my laboratory to study Fe(II) lifetimes and photoproduction under conditions typical of high latitude waters. The findings of this study suggest that, in contrast to results observed during mesoscale iron addition experiments, steady-state levels of Fe(II) are likely to remain low (below detection) even within a significant gradient in dissolved Fe concentrations produced as a result of natural iron enrichment processes. Fe(II) is likely to be produced, however, as a reactive intermediate associated with photochemical reactions in surface waters. While Fe(II) lifetimes measured in the field in this study were commensurate with those determined in previously published Southern Ocean work, Fe(II) lifetimes reflective of realistic Southern Ocean environmental conditions have proven difficult to determine in a laboratory setting, due to contamination by trace levels of H2O2. Laboratory experiments demonstrated that direct ligand-to-metal charge transfer reactions of strong Fe(III)-organic complexes do appear to be a viable source of available Fe(II) in Antarctic waters, and further studies are needed to characterize the temperature dependence of this phenomenon.« less

Adsorption of Pb(II), Cu(II), Cd(II), Zn(II), Ni(II), Fe(II), and As(V) on bacterially produced metal sulfides.

PubMed

Jong, Tony; Parry, David L

2004-07-01

The adsorption of Pb(II), Cu(II), Cd(II), Zn(II), Ni(II), Fe(II) and As(V) onto bacterially produced metal sulfide (BPMS) material was investigated using a batch equilibrium method. It was found that the sulfide material had adsorptive properties comparable with those of other adsorbents with respect to the specific uptake of a range of metals and, the levels to which dissolved metal concentrations in solution can be reduced. The percentage of adsorption increased with increasing pH and adsorbent dose, but decreased with increasing initial dissolved metal concentration. The pH of the solution was the most important parameter controlling adsorption of Cd(II), Cu(II), Fe(II), Ni(II), Pb(II), Zn(II), and As(V) by BPMS. The adsorption data were successfully modeled using the Langmuir adsorption isotherm. Desorption experiments showed that the reversibility of adsorption was low, suggesting high-affinity adsorption governed by chemisorption. The mechanism of adsorption for the divalent metals was thought to be the formation of strong, inner-sphere complexes involving surface hydroxyl groups. However, the mechanism for the adsorption of As(V) by BPMS appears to be distinct from that of surface hydroxyl exchange. These results have important implications to the management of metal sulfide sludge produced by bacterial sulfate reduction.

Computer program for determination of concentrations of trace elements in components of water systems by nondestructive activation analysis (in German)

DOE Office of Scientific and Technical Information (OSTI.GOV)

Slavic, I.; Draskovic, R.; Tasovac, T.

1973-03-01

A computer program for the determination of trace elements in components of the water systems bed material, suspended material, dissolved substances, plankton, algae) by nondestructive activation analysis was developed. Results of the determination of Cr, Sb, Sc, Fe, Co, Na, and La concentrations in suspended materials from the Danube river, obtained by interpretation of data with a CDC- 3600 computer (64 k words), are presented. (auth)

Oxidation of naturally reduced uranium in aquifer sediments by dissolved oxygen and its potential significance to uranium plume persistence

NASA Astrophysics Data System (ADS)

Davis, J. A.; Smith, R. L.; Bohlke, J. K.; Jemison, N.; Xiang, H.; Repert, D. A.; Yuan, X.; Williams, K. H.

2015-12-01

The occurrence of naturally reduced zones is common in alluvial aquifers in the western U.S.A. due to the burial of woody debris in flood plains. Such reduced zones are usually heterogeneously dispersed in these aquifers and characterized by high concentrations of organic carbon, reduced mineral phases, and reduced forms of metals, including uranium(IV). The persistence of high concentrations of dissolved uranium(VI) at uranium-contaminated aquifers on the Colorado Plateau has been attributed to slow oxidation of insoluble uranium(IV) mineral phases found in association with these reducing zones, although there is little understanding of the relative importance of various potential oxidants. Four field experiments were conducted within an alluvial aquifer adjacent to the Colorado River near Rifle, CO, wherein groundwater associated with the naturally reduced zones was pumped into a gas-impermeable tank, mixed with a conservative tracer (Br-), bubbled with a gas phase composed of 97% O2 and 3% CO2, and then returned to the subsurface in the same well from which it was withdrawn. Within minutes of re-injection of the oxygenated groundwater, dissolved uranium(VI) concentrations increased from less than 1 μM to greater than 2.5 μM, demonstrating that oxygen can be an important oxidant for uranium in such field systems if supplied to the naturally reduced zones. Dissolved Fe(II) concentrations decreased to the detection limit, but increases in sulfate could not be detected due to high background concentrations. Changes in nitrogen species concentrations were variable. The results contrast with other laboratory and field results in which oxygen was introduced to systems containing high concentrations of mackinawite (FeS), rather than the more crystalline iron sulfides found in aged, naturally reduced zones. The flux of oxygen to the naturally reduced zones in the alluvial aquifers occurs mainly through interactions between groundwater and gas phases at the water table. Seasonal variations of the water table at the Rifle, CO site may play an important role in introducing oxygen into the system. Although oxygen was introduced directly to the naturally reduced zones in these experiments, delivery of oxidants to the system may also be controlled by other oxidative pathways in which oxygen plays an indirect role.

Mechanisms for Fe(III) oxide reduction in sedimentary environments

USGS Publications Warehouse

Nevin, Kelly P.; Lovely, Derek R.

2002-01-01

Although it was previously considered that Fe(III)-reducing microorganisms must come into direct contact with Fe(III) oxides in order to reduce them, recent studies have suggested that electron-shuttling compounds and/or Fe(III) chelators, either naturally present or produced by the Fe(III)-reducing microorganisms themselves, may alleviate the need for the Fe(III) reducers to establish direct contact with Fe(III) oxides. Studies with Shewanella alga strain BrY and Fe(III) oxides sequestered within microporous beads demonstrated for the first time that this organism releases a compound(s) that permits electron transfer to Fe(III) oxides which the organism cannot directly contact. Furthermore, as much as 450 w M dissolved Fe(III) was detected in cultures of S. alga growing in Fe(III) oxide medium, suggesting that this organism releases compounds that can solublize Fe(III) from Fe(III) oxide. These results contrast with previous studies, which demonstrated that Geobacter metallireducens does not produce electron-shuttles or Fe(III) chelators. Some freshwater aquatic sediments and groundwaters contained compounds, which could act as electron shuttles by accepting electrons from G. metallireducens and then transferring the electrons to Fe(III). However, other samples lacked significant electron-shuttling capacity. Spectroscopic studies indicated that the electron-shuttling capacity of the waters was not only associated with the presence of humic substances, but water extracts of walnut, oak, and maple leaves contained electron-shuttling compounds did not appear to be humic substances. Porewater from a freshwater aquatic sediment and groundwater from a petroleum-contaminated aquifer contained dissolved Fe(III) (4-16 w M), suggesting that soluble Fe(III) may be available as an electron acceptor in some sedimentary environments. These results demonstrate that in order to accurately model the mechanisms for Fe(III) reduction in sedimentary environments it will be necessary to have information on the concentrations of electron-shuttling compounds and possibly Fe(III) ligands. Furthermore, as it is now apparent that different genera of Fe(III)-reducing microorganisms may reduce Fe(III) via different mechanisms, knowledge of which Fe(III)-reducing microorganisms predominate in the environment of interest is essential in order to model this process appropriately.

Dust in an acidified ocean: iron bioavailability, phytoplankton growth and DMS

NASA Astrophysics Data System (ADS)

Mélançon, J.; Levasseur, M.; Lizotte, M.; Scarratt, M. G.; Tremblay, J. E.; Tortell, P. D.; Yang, G.; Shi, G. Y.; Gao, H.; Semeniuk, D.; Robert, M.; Arychuk, M.; Johnson, K.; Sutherland, N.; Davelaar, M.; Nemcek, N.; Pena, A.; Richardson, W.

2015-12-01

Ocean acidification (OA) is likely to have an effect on the fertilizing potential of desert dust in high-nutrient, low-chlorophyll oceanic regions, either by modifying Fe speciation and bioavailability, or by altering phytoplankton Fe requirements and acquisition. To address this issue, short incubations (4 days) of northeast subarctic Pacific waters enriched with either FeSO4 or dust, and maintained at pH 8.0 (in situ) and 7.8 were conducted in August 2010. We assessed the impact of a decrease in pH on dissolved Fe concentration, phytoplankton biomass, taxonomy and productivity, and the production of dimethylsulfide (DMS) and its algal precursor dimethylsulfoniopropionate (DMSP). Chlorophyll a (chl a) remained unchanged in the controls and doubled in both the FeSO4-enriched and dust-enriched incubations, confirming the Fe-limited status of the plankton assemblage during the experiment. In the acidified treatments, a significant reduction (by 16-38%) of the final concentration of chl a was measured compared to their non-acidified counterparts, and a 15% reduction in particulate organic carbon (POC) concentration was measured in the dust-enriched acidified treatment compared to the dust-enriched non-acidified treatment. FeSO4 and dust additions had a fertilizing effect mainly on diatoms and cyanobacteria. Lowering the pH affected mostly the haptophytes, but pelagophyte concentrations were also reduced in some acidified treatments. Acidification did not significantly alter DMSP and DMS concentrations. These results show that dust deposition events in a low-pH iron-limited Northeast subarctic Pacific are likely to stimulate phytoplankton growth to a lesser extent than in today's ocean during the few days following fertilization and point to a low initial sensitivity of the DMSP and DMS dynamics to OA.

High Temperature Oxidation of Hot-Dip Aluminized T92 Steels

NASA Astrophysics Data System (ADS)

Abro, Muhammad Ali; Hahn, Junhee; Lee, Dong Bok

2018-03-01

The T92 steel plate was hot-dip aluminized, and oxidized in order to characterize the high-temperature oxidation behavior of hot-dip aluminized T92 steel. The coating consisted of Al-rich topcoat with scattered Al3Fe grains, Al3Fe-rich upper alloy layer with scattered (Al, Al5Fe2, AlFe)-grains, and Al5Fe2-rich lower alloy layer with scattered (Al5Fe2, AlFe)-grains. Oxidation at 800 °C for 20 h formed (α-Al2O3 scale)/(AlFe layer)/(AlFe3 layer)/(α-Fe(Al) layer), while oxidation at 900 °C for 20 h formed (α-Al2O3 scale plus some Fe2O3)/(AlFe layer)/(AlFe3 layer)/(α-Fe(Al) layer) from the surface. During oxidation, outward migration of all substrate elements, inward diffusion of oxygen, and back and forth diffusion of Al occurred according to concentration gradients. Also, diffusion transformed and broadened AlFe and AlFe3 layers dissolved with some oxygen and substrate alloying elements. Hot-dip aluminizing improved the high-temperature oxidation resistance of T92 steel through preferential oxidation of Al at the surface.

High Temperature Oxidation of Hot-Dip Aluminized T92 Steels

NASA Astrophysics Data System (ADS)

Abro, Muhammad Ali; Hahn, Junhee; Lee, Dong Bok

2018-05-01

The T92 steel plate was hot-dip aluminized, and oxidized in order to characterize the high-temperature oxidation behavior of hot-dip aluminized T92 steel. The coating consisted of Al-rich topcoat with scattered Al3Fe grains, Al3Fe-rich upper alloy layer with scattered (Al, Al5Fe2, AlFe)-grains, and Al5Fe2-rich lower alloy layer with scattered (Al5Fe2, AlFe)-grains. Oxidation at 800 °C for 20 h formed (α-Al2O3 scale)/(AlFe layer)/(AlFe3 layer)/(α-Fe(Al) layer), while oxidation at 900 °C for 20 h formed (α-Al2O3 scale plus some Fe2O3)/(AlFe layer)/(AlFe3 layer)/(α-Fe(Al) layer) from the surface. During oxidation, outward migration of all substrate elements, inward diffusion of oxygen, and back and forth diffusion of Al occurred according to concentration gradients. Also, diffusion transformed and broadened AlFe and AlFe3 layers dissolved with some oxygen and substrate alloying elements. Hot-dip aluminizing improved the high-temperature oxidation resistance of T92 steel through preferential oxidation of Al at the surface.

The Rusty Sink: Iron Promotes the Preservation of Organic Matter in Sediments

NASA Astrophysics Data System (ADS)

Lalonde, K. M.; Mucci, A.; Moritz, A.; Ouellet, A.; Gelinas, Y.

2011-12-01

The biogeochemical cycles of iron (Fe) and organic carbon (OC) are strongly interlinked. In oceanic waters, organic ligands have been shown to control the concentration of dissolved Fe [1], whereas in soils, solid Fe phases provide a sheltering and preservative effect for organic matter [2]. Until now however, the role of iron in the preservation of OC in sediments has not been clearly established. Here we show that 21.5 ± 8.6% of the OC in sediments is directly bound to reactive iron phases, which promote the preservation of OC in sediments. Iron-bound OC represents a global mass of 19 to 45 × 10^15 g of OC in surface marine sediments. This pool of OC is different from the rest of sedimentary OC, with 13C and nitrogen-enriched organic matter preferentially bound to Fe which suggests that biochemical fractionation occurs with OC-Fe binding. Preferential binding also affects the recovery of high molecular weight lipid biomarkers and acidic lignin oxidation products, changing the environmental message of proxies derived from these biomarkers. [1] Johnson, K. S., Gordon, R. M. & Coale, K. H. What controls dissolved iron in the world ocean? Marine Chemistry 57, 137-161 (1997). [2] Kaiser, K. & Guggenberger, G. The role of DOM sorption to mineral surfaces in the preservation of organic matter in soils. Organic Geochemistry 31, 711-725 (2000).

Microbial Immobilization of Si, Mn, Fe, and Sr Ions in the Nacreous Layer of Sinohyliopsis schlegeli and Environmental Factors

NASA Astrophysics Data System (ADS)

Tazaki, Kazue; Morii, Issei

Environmental changes recorded in the shell nacre of Sinohyliopsis schlegeli were observed with elemental factors of characteristic water and nutrition for eight months in a cultivated drainage pond at Kanazawa University, Ishikawa Prefecture, Japan. Tetracycline as an indicator was injected into the shell nacre once every month from May to November in 2007. Water qualities such as the pH, redox potential, electrical conductivity, dissolved oxygen concentration, and water temperature were measured periodically, and the suspended solids in the water were removed by filtration for optical microscopy, X-ray fluorescence analysis, and scanning electron microscopy-energy dispersive X-ray (SEM-EDX) observations. X-ray fluorescence chemical analysis of shell nacre indicated layers with strong tetracycline accumulation corresponding to high concentrations of Si, Mn, Fe, and Sr ions. The redox potential and dissolved oxygen concentration measurements supported the existence of layers in the nacre. The suspended materials in the drainage pond water comprised mainly of Si, Mn, and Fe elements, which were the same elements involved in microbial immobilization in the shell nacre during the summer of 2007. SEM-EDX analyses confirmed that the ions originated from diatoms, Siderocapsa sp. and Gallionella ferruginea in the stomach. There was little microbial immobilization of the ions in winter. The results suggested elemental immobilization in the layered shell nacre and indicated that Sinohyliopsis schlegeli fed on the ions, to grow the nacre during summer. Sinohyliopsis schlegeli with these biogenic oxides might contribute to the scavenging of heavy metals in natural water.

A tale of two gyres: Contrasting distributions of dissolved cobalt and iron in the Atlantic Ocean during an Atlantic Meridional Transect (AMT-19)

NASA Astrophysics Data System (ADS)

Shelley, Rachel U.; Wyatt, Neil J.; Tarran, Glenn A.; Rees, Andrew P.; Worsfold, Paul J.; Lohan, Maeve C.

2017-11-01

Cobalt (Co) and iron (Fe) are essential for phytoplankton nutrition, and as such constitute a vital link in the marine biological carbon pump. Atmospheric deposition is an important, and in some places the dominant, source of trace elements (TEs) to the global ocean. Dissolved cobalt (dCo) and iron (dFe) were determined along an Atlantic Meridional Transect (AMT-19; Oct/Nov 2009) between 50°N and 40°S in the upper 150 m in order to investigate the behaviour and distribution of these two essential, bioactive TEs. During AMT-19, large differences in the distributions of dCo and dFe were observed. In the North Atlantic gyre provinces, extremely low mixed layer dCo concentrations (23 ± 9 pM) were observed, which contrasts with the relatively high mixed layer dFe concentrations (up to 1.0 nM) coincident with the band of highest atmospheric deposition (∼5-30°N). In the South Atlantic gyre, the opposite trend was observed, with relatively high dCo (55 ± 18 pM) observed throughout the water column, but low dFe concentrations (0.29 ± 0.08 nM). Given that annual dust supply is an order of magnitude greater in the North than the South Atlantic, the dCo distribution was somewhat unexpected. However, the distribution of dCo shows similarities with the distribution of phosphate (PO43-) in the euphotic zone of the Atlantic Ocean, where the North Atlantic gyre is characterised by chronically low PO4, and higher concentrations are observed in the South Atlantic gyre (Mather et al., 2008), suggesting the potential for a similar biological control of dCo distributions. Inverse correlations between dCo and Prochlorococcus abundance in the North Atlantic gyre provinces, combined with extremely low dCo where nitrogen fixation rates were highest (∼20-28°N), suggests the dominance of biological controls on dCo distributions. The contrasting dCo and dFe distributions in the North and South Atlantic gyres provides insights into the differences between the dominant controls on the distribution of these two bioactive trace metals in the central Atlantic Ocean.

Removal of arsenic from synthetic acid mine drainage by electrochemical pH adjustment and coprecipitation with iron hydroxide.

PubMed

Wang, Jenny Weijun; Bejan, Dorin; Bunce, Nigel J

2003-10-01

Acid mine drainage (AMD), which is caused by the biological oxidation of sulfidic materials, frequently contains arsenic in the form of arsenite, As(III), and/or arsenate, As(V), along with much higher concentrations of dissolved iron. The present work is directed toward the removal of arsenic from synthetic AMD by raising the pH of the solution by electrochemical reduction of H+ to elemental hydrogen and coprecipitation of arsenic with iron(III) hydroxide, following aeration of the catholyte. Electrolysis was carried out at constant current using two-compartment cells separated with a cation exchange membrane. Four different AMD model systems were studied: Fe(III)/As(V), Fe(III)/As(III), Fe(II)/As(V), and Fe(II)/As(III) with the initial concentrations for Fe(III) 260 mg/L, Fe(II) 300 mg/L, As(V), and As(III) 8 mg/L. Essentially quantitative removal of arsenic and iron was achieved in all four systems, and the results were independent of whether the pH was adjusted electrochemically or by the addition of NaOH. Current efficiencies were approximately 85% when the pH of the effluent was 4-7. Residual concentrations of arsenic were close to the drinking water standard proposed by the World Health Organization (10 microg/L), far below the mine waste effluent standard (500 microg/L).

Formation of Fe(III) oxyhydroxide colloids in freshwater and brackish seawater, with incorporation of phosphate and calcium

NASA Astrophysics Data System (ADS)

Gunnars, Anneli; Blomqvist, Sven; Johansson, Peter; Andersson, Christian

2002-03-01

The formation of Fe(III) oxyhydroxide colloids by oxidation of Fe(II) and their subsequent aggregation to larger particles were studied in laboratory experiments with natural water from a freshwater lake and a brackish coastal sea. Phosphate was incorporated in the solid phase during the course of hydrolysis of iron. The resulting precipitated amorphous Fe(III) oxyhydroxide phases were of varying composition, depending primarily on the initial dissolved Fe/P molar ratio, but with little influence by salinity or concentration of calcium ions. The lower limiting Fe/P ratio found for the solid phase suggests the formation of a basic Fe(III) phosphate compound with a stoichiometric Fe/P ratio of close to two. This implies that an Fe/P stoichiometry of ≈2 ultimately limits the capacity of precipitating Fe(III) to fix dissolved phosphate at oxic/anoxic boundaries in natural waters. In contrast to phosphorus, the uptake of calcium seemed to be controlled by sorption processes at the surface of the iron-rich particles formed. This uptake was more efficient in freshwater than in brackish water, suggesting that salinity restrains the uptake of calcium by newly formed Fe(III) oxyhydroxides in natural waters. Moreover, salinity enhanced the aggregation rate of the colloids formed. The suspensions were stabilised by the presence of organic matter, although this effect was less pronounced in seawater than in freshwater. Thus, in seawater of 6 to 33 ‰S, the removal of particles was fast (removal half time < 200 h), whereas the colloidal suspensions formed in freshwater were stable (removal half time > 900 h). Overall, oxidation of Fe(II) and removal of Fe(III) oxyhydroxide particles were much faster in seawater than in freshwater. This more rapid turnover results in lower iron availability in coastal seawater than in freshwater, making iron more likely to become a limiting element for chemical scavenging and biologic production.

Phosphorus runoff from waste water treatment biosolids and poultry litter applied to agricultural soils.

PubMed

White, John W; Coale, Frank J; Sims, J Thomas; Shober, Amy L

2010-01-01

Differences in the properties of organic phosphorus (P) sources, particularly those that undergo treatment to reduce soluble P, can affect soil P solubility and P transport in surface runoff. This 2-yr field study investigated soil P solubility and runoff P losses from two agricultural soils in the Mid-Atlantic region after land application of biosolids derived from different waste water treatment processes and poultry litter. Phosphorus speciation in the biosolids and poultry litter differed due to treatment processes and significantly altered soil P solubility and dissolved reactive P (DRP) and bioavailable P (FeO-P) concentrations in surface runoff. Runoff total P (TP) concentrations were closely related to sediment transport. Initial runoff DRP and FeO-P concentrations varied among the different biosolids and poultry litter applied. Over time, as sediment transport declined and DRP concentrations became an increasingly important component of runoff FeO-P and TP, total runoff P was more strongly influenced by the type of biosolids applied. Throughout the study, application of lime-stabilized biosolids and poultry litter increased concentrations of soil-soluble P, readily desorbable P, and soil P saturation, resulting in increased DRP and FeO-P concentrations in runoff. Land application of biosolids generated from waste water treatment processes that used amendments to reduce P solubility (e.g., FeCl(3)) did not increase soil P saturation and reduced the potential for DRP and FeO-P transport in surface runoff. These results illustrate the importance of waste water treatment plant process and determination of specific P source coefficients to account for differential P availability among organic P sources.

Atmospheric Dissolved Iron Depostiion to the Global Oceans: Effects of Oxalate-Promoted Fe Dissolution, Photochemical Redox Cycling, and Dust Mineralogy

NASA Technical Reports Server (NTRS)

Johnson, M. S.; Meskhidze, N.

2013-01-01

Mineral dust deposition is suggested to be a significant atmospheric supply pathway of bioavailable iron (Fe) to Fe-depleted surface oceans. In this study, mineral dust and dissolved Fe (Fed) deposition rates are predicted for March 2009 to February 2010 using the 3-D chemical transport model GEOS-Chem implemented with a comprehensive dust-Fe dissolution scheme. The model simulates Fed production during the atmospheric transport of mineral dust taking into account inorganic and organic (oxalate)-promoted Fe dissolution processes, photochemical redox cycling between ferric (Fe(III)) and ferrous (Fe(II)) forms of Fe, dissolution of three different Fe-containing minerals (hematite, goethite, and aluminosilicates), and detailed mineralogy of windblown dust from the major desert regions. Our calculations suggest that during the yearlong simulation is approximately 0.26 Tg (1 Tg = 1012 g) of Fed was deposited to global oceanic regions. Compared to simulations only taking into account proton-promoted Fe dissolution, the addition of oxalate to the dust-Fe mobilization scheme increased total annual model-predicted Fed deposition to global oceanic regions by approximately 75%. The implementation of Fe(II)/Fe(III) photochemical redox cycling in the model allows for the distinction between different oxidation states of deposited Fed. Our calculations suggest that during the daytime, large fractions of Fed deposited to the global oceans is likely to be in Fe(II) form, while nocturnal fluxes of Fed are largely in Fe(III) form. Model simulations also show that atmospheric fluxes of Fed can be strongly influenced by the mineralogy of Fe-containing compounds. This study shows that Fed deposition to the oceans is controlled by total dust-Fe mass concentrations, mineralogy, the surface area of dust particles, atmospheric chemical composition, cloud processing, and meteorological parameters and exhibits complex and spatiotemporally variable patterns. Our study suggests that the explicit model representation of individual processes leading to Fed production within mineral dust are needed to improve the understanding of the atmospheric Fe cycle, and quantify the effect of dust-Fe on ocean biological productivity, carbon cycle, and climate.

Arsenic Mobilization Influenced By Iron Reduction And Sulfidogenesis Under Dynamic Flow

NASA Astrophysics Data System (ADS)

Kocar, B. D.; Stewart, B. D.; Herbel, M.; Fendorf, S.

2004-12-01

Sulfidogenesis and iron reduction are ubiquitous processes that occur in a variety of anoxic subsurface and surface environments, which profoundly impact the cycling of arsenic. Of the iron (hydr)oxides, ferrihydrite possesses one of the highest capacities to retain arsenic, and is globally distributed within soils and sediments. Upon dissimilatory iron reduction, ferrihydrite may transform to lower surface area minerals, such as goethite and magnetite, which decreases arsenic retention, thus enhancing its transport. Here we examine how arsenic retained on ferrihydrite is mobilized under dynamic flow in the presence of Sulfurosprillum barnesii strain SES-3, a bacteria capable of reducing both As(V) and Fe(III). Ferrihydrite coated sands, loaded with 150 mg kg-1 As(V), were inoculated with S. barnesii, packed into a column and reacted with a synthetic groundwater solution. Within several days after initiation of flow, the concentration of arsenic in the column effluent increased dramatically coincident with the mineralogical transformation of ferrihydrite and As(V) reduction to As(III). Following the initial pulse of arsenic, effluent concentration then declined to less than 10 μ M. Thus, arsenic release into the aqueous phase is contingent upon the incongruent reduction of As(V) and Fe(III) as mediated by biological activity. Reaction of abiotically or biotically generated dissolved sulfide with iron (hydr)oxides may have a dramatic influence on the fate of arsenic within surface and subsurface environments. Accordingly, we examined the reaction of dissolved bisulfide and iron (hydr)oxide complexed with arsenic in both batch and column systems. Low ratios of sulfide to iron in batch reaction systems result in the formation of elemental sulfur and concomitant arsenic release from the iron (hydr)oxide surface. High sulfide to iron ratios, in contrast, appear to favor the formation of iron and arsenic sulfides. Our findings demonstrate that iron (hydr)oxides may quench reactions between sulfide and constituents sorbed to iron (hydr)oxide surfaces, forming elemental sulfur as opposed to sulfide-arsenic complexes. In addition, reductive transformation of iron (hydr)oxide by dissolved sulfide may release sorbed constituents. Hence, moderate to low concentrations of dissolved sulfide in association with iron (hydr)oxides may inhibit sequestration of important contaminants that are attenuated by Fe(III) and/or S(-II) bearing phases.

Humic substances and trace metals associated with Fe and Al oxides deposited in an acidic mountain stream

USGS Publications Warehouse

McKnight, Diane M.; Wershaw, R. L.; Bencala, K.E.; Zellweger, G.W.; Feder, G.L.

1992-01-01

Hydrous iron and aluminum oxides are deposited on the streambed in the confluence of the Snake River and Deer Creek, two streams in the Colorado Rocky Mountains. The Snake River is acidic and has high concentrations of dissolved Fe and Al. These metals precipitate at the confluence with the pristine, neutral pH, Deer Creek because of the greater pH (4.5-6.0) in the confluence. The composition of the deposited oxides changes consistently with distance downstream, with the most upstream oxide samples having the greatest Fe and organic carbon content. Fulvic acid accounts for most of the organic content of the oxides. Results indicate that streambed oxides in the confluence are not saturated with respect to their capacity to sorb dissolved humic substances from streamwater. The contents of several trace metals (Mn, Zn, Cu, Pb, Ni and Co) also decrease with distance downstream and are correlated with both the Fe and organic carbon contents. Strong metal-binding sites associated with the sorbed fulvic acid are more than sufficient to account for the trace metal content of the oxides. Complexation of trace metals by sorbed fulvic acid may explain the observed downstream decrease in trace metal content.

Emissions of Fe(II) and its kinetic of oxidation at Tagoro submarine volcano, El Hierro (Canary Islands)

NASA Astrophysics Data System (ADS)

González-Dávila, M.; Santana-González, C.; Santana-Casiano, J. M.

2017-12-01

The eruptive process that took place in October 2011 in the submarine volcano Tagoro off the Island of El Hierro (Canary Island) and the subsequent degasification stage, five months later, have increased the concentration of TdFe(II) (Total dissolved iron(II)) in the waters nearest to the volcanic edifice. In order to detect any variation in concentrations of TdFe(II) due to hydrothermal emissions, three cruises were carried out two years after the eruptive process in October 2013, March 2014, May 2015, March 2016 and November 2016. The results from these cruises confirmed important positive anomalies in TdFe(II), which coincided with negatives anomalies in pHF,is (pH in free scale, at in situ conditions) located in the proximity of the main cone. Maximum values in TdFe(II) both at the surface, associated to chlorophyll a maximum, and at the sea bottom, were also observed, showing the important influence of organic complexation and particle re-suspension processes. Temporal variability studies were carried out over periods ranging from hours to days in the stations located over the main and two secondary cones in the volcanic edifice with positive anomalies in TdFe(II) concentrations and negative anomalies in pHF,is values. Observations showed an important variability in both pHF,is and TdFe(II) concentrations, which indicated the volcanic area was affected by a degasification process that remained in the volcano after the eruptive phase had ceased. Fe(II) oxidation kinetic studies were also undertaken in order to analyze the effects of the seawater properties in the proximities of the volcano on the oxidation rate constants and t1/2 (half-life time) of ferrous iron. The increased TdFe(II) concentrations and the low associated pHF,is values acted as an important fertilization event in the seawater around the Tagoro volcano at the Island of El Hierro providing optimal conditions for the regeneration of the area.

Trace element fractionation and transport in boreal rivers and soil porewaters of permafrost-dominated basaltic terrain in Central Siberia

NASA Astrophysics Data System (ADS)

Pokrovsky, O. S.; Schott, J.; Dupré, B.

2006-07-01

The chemical status of ˜40 major and trace elements (TE) and organic carbon (OC) in pristine boreal rivers draining the basaltic plateau of Central Siberia (Putorana) and interstitial solutions of permafrost soils was investigated. Water samples were filtered in the field through progressively decreasing pore size (5 μm → 0.22 μm → 0.025 μm → 10 kDa → 1 kDa) using cascade frontal filtration technique. Most rivers and soil porewaters exhibit 2-5 times higher than the world average concentration of dissolved (i.e., <0.22 μm) iron (0.03-0.4 mg/L), aluminum (0.03-0.4 mg/L), OC (10-20 mg/L) and various trace elements that are usually considered as immobile in weathering processes (Ti, Zr, Ga, Y, REEs). Ultrafiltration revealed strong relationships between concentration of TE and that of colloidal Fe and Al. According to their partition during filtration and association with colloids, two groups of elements can be distinguished: (i) those weakly dependent on ultrafiltration and that are likely to be present as truly dissolved inorganic species (Li, Na, K, Si, Mn, Mo, Rb, Cs, As, Sb) or, partially (20-30%) associated with small size Fe- and Al-colloids (Ca, Mg, Sr, Ba) and to small (<1-10 kDa) organic complexes (Co, Ni, Cu, Zn), and (ii) elements strongly associated with colloidal iron and aluminum in all ultrafiltrates largely present in 1-100 kDa fraction (Ga, Y, REEs, Pb, V, Cr, Ti, Ge, Zr, Th, U). TE concentrations and partition coefficients did not show any detectable variations between different colloidal fractions for soil porewaters, suprapermafrost flow and surface streams. TE concentration measurements in river suspended particles demonstrated significant contribution (i.e., ⩾30%) of conventionally dissolved (<0.22 μm) forms for usually "immobile" elements such as divalent transition metals, Cd, Pb, V, Sn, Y, REEs, Zr, Hf, Th. The Al-normalized accumulation coefficients of TE in vegetation litter compared to basalts achieve 10-100 for B, Mn, Zn, As, Sr, Sn, Sb, and the larch litter degradation is able to provide the major contribution to the annual dissolved flux of most trace elements. It is hypothesized that the decomposition of plant litter in the topsoil horizon leads to Fe(III)-, Al-organic colloids formation and serves as an important source of elements in downward percolating fluids.

The role of copper and oxalate in the redox cycling of iron in atmospheric waters

NASA Astrophysics Data System (ADS)

Sedlak, David L.; Hoigné, Jürg

During daytime, the redox cycling of dissolved iron compounds in atmospheric waters, and the related in-cloud transformations of photooxidants, are affected by reactions of Fe and Cu with hydroperoxy (HO 2) and superoxide (O 2-) radicals and the photoreduction of Fe(III)-oxalato complexes. We have investigated several of the important chemical reactions in this redox cycle, through laboratory simulation of the system, using γ-radiation to produce HO 2/O 2-. At concentrations comparable to those measured in atmospheric waters, the redox cycling of Fe was dramatically affected by the presence of oxalate and trace concentrations of Cu. At concentrations more than a hundred times lower than Fe, Cu consumed most of the HO 2/O 2-, and cycled between the Cu(II) and Cu(I) forms. Cu + reacted with FeOH 2+ to produce Fe(II) and Cu(II), with a second order rate constant of approximately 3 × 10 7 M -1s -1. The presence of oxalate resulted in the formation of Fe(III)-oxalato complexes that were essentially unreactive with HO 2/O 2-. Only at high oxalate concentrations was the Fe(II)C 2O 4 complex also formed, and it reacted relatively rapidly with hydrogen peroxide ( k = (3.1 ± 0.6) × 10 4 M -1s -1). Simulations incorporating measurements for other redox mechanisms, including oxidation by ozone, indicate that, during daytime, Fe should be found mostly in the ferrous oxidation state, and that reactions of FeOH 2+ with Cu(I) and HO 2/O 2-, and to a lesser degree, the photolysis of Fe(III)-oxalato complexes, are important mechanisms of Fe reduction in atmospheric waters. The catalytic effect of Cu(II)/Cu(I) and Fe(III)/Fe(II) should also significantly increase the sink function of the atmospheric liquid phase for HO 2 present in a cloud. A simple kinetic model for the reactions of Fe, Cu and HO 2/O 2-, accurately predicted the changes in Fe oxidation states that occurred when authentic fogwater samples were exposed to HO 2/O 2-.

Geochemistry of shallow ground water in coastal plain environments in the southeastern United States: Implications for aquifer susceptibility

USGS Publications Warehouse

Tesoriero, A.J.; Spruill, T.B.; Eimers, J.L.

2004-01-01

Ground-water chemistry data from coastal plain environments have been examined to determine the geochemical conditions and processes that occur in these areas and assess their implications for aquifer susceptibility. Two distinct geochemical environments were studied to represent a range of conditions: an inner coastal plain setting having more well-drained soils and lower organic carbon (C) content and an outer coastal plain environment that has more poorly drained soils and high organic C content. Higher concentrations of most major ions and dissolved inorganic and organic C in the outer coastal plain setting indicate a greater degree of mineral dissolution and organic matter oxidation. Accordingly, outer coastal plain waters are more reducing than inner coastal plain waters. Low dissolved oxygen (O2) and nitrate (NO 3-) concentrations and high iron (Fe) concentrations indicate that ferric iron (Fe (III)) is an important electron acceptor in this setting, while dissolved O2 is the most common terminal electron acceptor in the inner coastal plain setting. The presence of a wide range of redox conditions in the shallow aquifer system examined here underscores the importance of providing a detailed geochemical characterization of ground water when assessing the intrinsic susceptibility of coastal plain settings. The greater prevalence of aerobic conditions in the inner coastal plain setting makes this region more susceptible to contamination by constituents that are more stable under these conditions and is consistent with the significantly (p<0.05) higher concentrations of NO3- found in this setting. Herbicides and their transformation products were frequently detected (36% of wells sampled), however concentrations were typically low (<0.1 ??g/L). Shallow water table depths often found in coastal plain settings may result in an increased risk of the detection of pesticides (e.g., alachlor) that degrade rapidly in the unsaturated zone.

Use of TEVA resin for the determination of U isotopes in water samples by Q-ICP-MS.

PubMed

Tagami, K; Uchida, S

2004-01-01

In order to measure uranium isotopic mass ratio in natural water samples by Q-ICP-MS, an application of TEVA resin (Eichrom) was studied to separate and concentrate U. After being evaporated to dryness, the sample residue was dissolved in 6 M HCl, then, TEVA extraction was carried out. U extracted on the resin could be removed with 20 ml of 1 M HCl (U fraction) when Fe content was lower than 2 mg. U recovery in U fraction showed a negative correlation with Fe content in the samples.

Contrasting Physiological and Proteomic Adaptations to Iron and/or Copper Limitation in Two Strains of the Same Open Ocean Diatom Thalassiosira oceanica

NASA Astrophysics Data System (ADS)

Schuback, N.; Hippmann, A.; Maldonado, M. T.; Allen, A. E.; McCrow, J.; Foster, L. J.; Green, B. R.; Alami, M.

2016-02-01

Iron plays a significant role in controlling marine primary productivity. Despite that extremely low dissolved iron (Fe) concentrations are found in Fe-limited regions, some phytoplankton are able to survive and thrive. Two strains of the model oceanic diatom Thalassiosira oceanica, TO 1003 and TO 1005, have both been used in previous studies to characterize adaptations to iron limitation. These studies have shown that T. oceanica has lowered its Fe requirements and increased its Fe acquisition efficiency compared to coastal counterparts. Both strategies may impose a higher cellular copper (Cu) demand. However, the underlying biochemical adaptations in these oceanic diatoms remain unknown. Recently, the genome, as well as the first proteomic and transcriptomic analyses of T. oceanica 1005 grown under different Fe levels, were published. To further our understanding of the interplay between Fe- and Cu- physiology in open ocean diatoms, we examined an array of physiological responses to varying degrees of Fe-, Cu- and Fe/Cu co-limitation in both strains. We also determined the differential expression of proteins using stable isotope labeling and LC-MS/MS proteomic analysis. The two strains, TO 1003 and TO 1005, need markedly different metal concentrations in the media. TO1003 requires 30% less Cu to sustain its optimal growth and less than 1/10th of the minimum Cu that is needed by TO 1005 to survive. In contrast, TO 1005 is able to grow with less Fe available in the media. The physiological and proteomic responses of these two strains when acclimated to low Fe and/or Cu concentrations will be presented. The evolutionary implications will be discussed.

Iron Isotope Variations in Reduced Groundwater and in Drinking Water Supplies: A Case Study of Hanoi, Vietnam

NASA Astrophysics Data System (ADS)

Teutsch, N.; Berg, M.; von Gunten, U.; Halliday, A.

2004-12-01

In reduced groundwater iron is involved in biotic and abiotic transformation processes, both of which could lead to iron isotope fractionation. The reduced groundwater aquifers in the area of the Vietnamese capital of Hanoi are the main drinking water sources for the city. These groundwaters contain arsenic, which imposes a serious health threat to millions of people. Dissolved arsenic is related to the reducing conditions prevalent in the groundwater, and iron and arsenic contents are correlated in the sediments. We are employing iron isotope composition as a tool to better understand the processes leading to the transformation of iron in the groundwater and its role in various biogeochemical processes in reduced environments. Drinking water is supplied to the city of Hanoi from several water treatment plants (WTP) which pump the raw groundwater from a lower aquifer, while the rural surroundings pump untreated groundwater from an upper aquifer by private tubewells. Surface water from the Red River delta is the main source of recharge to these two aquifers. Due to high content of particulate natural organic matter (NOM) in the sediment leading to extensive microbial activity, the groundwaters are anoxic and rich in dissolved iron(II). The iron(II) removal in the WTPs is carried by a multi-step treatment including aeration, settling, filtration, and chlorination. We have collected natural groundwater samples for isotopic analysis from two aquifers at several locations, a groundwater depth profile and its corresponding sediment phases from the upper aquifer and the underlying aquitard, raw and treated water from several WTPs, as well as the corresponding iron(III) precipitates. The iron concentrations of groundwaters analysed in this study range from 3 to 28 mg/L and δ 57Fe (57/54 deviation from IRMM 014) values vary between -1.2 and +1.5 ‰ . The sediment depth profile has a δ 57Fe around +0.3 ‰ , which implies that the high values obtained in the groundwater nearby (+0.9 - +1.2 ‰ ) cannot be explained by a simple reductive dissolution process, which would be expected to favour the lighter Fe isotopes. Removal of iron in the WTP is followed by a strong decrease of δ 57Fe, probably due to formation of heavier Fe(III) phases. High δ 57Fe values are found in both aquifers and correspond to high concentrations of iron in the groundwater. We hypothesize that the iron isotopic variations observed so far are an indication for iron sources and transformation processes that could not be detected by only measuring dissolved iron concentrations. Current investigations will further explore this hypothesis.

Rare earth elements mobility processes in an AMD-affected estuary: Huelva Estuary (SW Spain).

PubMed

Lecomte, K L; Sarmiento, A M; Borrego, J; Nieto, J M

2017-08-15

Huelva Estuary is a transition zone where REE-rich acidic waters interact with saline-alkaline seawater. This mixing process influences the geochemical and mineralogical characteristics of particulate and dissolved fractions. The Tinto River has >11,000μgL -1 dissolved REE (pH=1.66), whereas seawater only reaches 8.75·10 -2 μgL -1 dissolved REE (pH=7.87). REE-normalized patterns in "pH<6 solutions" are parallel and show similarities, diminishing their concentration as pH increases. Sequential extraction performed on the generated precipitates of mixed solutions indicates that most REE are associated to the residual phase. In a second order, REE are associated with soluble salts at pH3 and 3.5 whereas in sediments generated at pH4 and 5, they are distributed in salts (1° extraction), poorly crystallized Fe-bearing minerals (schwertmannite, 3° extraction) and well crystallized Fe-bearing minerals (goethite - hematite, 4° extraction). Finally, precipitated REE are highest at pH6 newly formed minerals with a release to solution in higher pH. Copyright © 2017 Elsevier Ltd. All rights reserved.

Partition of heavy metals in a tropical river system impacted by municipal waste.

PubMed

Duc, Trinh Anh; Loi, Vu Duc; Thao, Ta Thi

2013-02-01

A research program was established to identify the governing factors for the partition coefficient (K(D)) of heavy metals between suspended particulate and dissolved phases in the Day River system a tropical, highly alluvial aquatic system, in Vietnam. The targeted river system, draining an urbanized-industrialized catchment where discharged wastewater is mostly untreated, could be separated into the least impacted, pristine area, and the most impacted, polluted area. Organic matter degradation was shown to govern the variation of parameters like total organic carbon, biochemical oxygen demand, chemical oxygen demand, nutrients, conductivity, or redox potential. Heavy metals in both dissolved and particulate phases were enriched in severely polluted area because of wastewater inflow that contains concentrated metals and intensification of metal influx from sediment. Results show log K(D) in the order Mn < As < Zn < Hg < Ni < Cu < Cd < Co < Pb < Cr < Fe and As < Zn < Ni < Mn < Cr < Cu < Co < Fe in the polluted zone and the pristine zone, respectively. A decreasing tendency of partition coefficients of 11 heavy metals considered from the pristine to the impacted zones was observed. Three explanations for the difference are: (1) increase of solubility of most heavy metals in low redox potential, (2) competition for the binding sites with major and minor cations, and (3) complexation with dissolved organic matter concentrated in municipal waste impacted water. Apart from domestic waste impact, statistical analysis has contributed to identify the influence of climate condition and hydrological regime to the partition of heavy metals in the area.

Annual suspended sediment and trace element fluxes in the Mississippi, Columbia, Colorado, and Rio Grande drainage basins

USGS Publications Warehouse

Horowitz, A.J.; Elrick, K.A.; Smith, J.J.

2001-01-01

Suspended sediment, sediment-associated, total trace element, phosphorus (P), and total organic carbon (TOC) fluxes were determined for the Mississippi, Columbia, Rio Grande, and Colorado Basins for the study period (the 1996, 1997, and 1998 water years) as part of the US Geological Survey's redesigned National Stream Quality Accounting Network (NASQAN) programme. The majority (??? 70%) of Cu, Zn, Cr, Ni, Ba, P, As, Fe, Mn, and Al are transported in association with suspended sediment; Sr transport seems dominated by the dissolved phase, whereas the transport of Li and TOC seems to be divided equally between both phases. Average dissolved trace element levels are markedly lower than reported during the original NASQAN programme; this seems due to the use of 'clean' sampling, processing, and analytical techniques rather than to improvements in water quality. Partitioning between sediment and water for Ag, Pb, Cd, Cr, Co, V, Be, As, Sb, Hg, and Ti could not be estimated due to a lack of detectable dissolved concentrations in most samples. Elevated suspended sediment-associated Zn levels were detected in the Ohio River Basin and elevated Hg levels were detected in the Tennessee River, the former may affect the mainstem Mississippi River, whereas the latter probably do not. Sediment-associated concentrations of Ag, Cu, Pb, Zn, Cd, Cr, Co, Ba, Mo, Sb, Hg, and Fe are markedly elevated in the upper Columbia Basin, and appear to be detectable (Zn, Cd) as far downstream as the middle of the basin. These elevated concentrations seem to result from mining and/or mining-related activities. Consistently detectable concentrations of dissolved Se were found only in the Colorado River Basin. Calculated average annual suspended sediment fluxes at the mouths of the Mississippi and Rio Grande Basins were below, whereas those for the Columbia and Colorado Basins were above previously published annual values. Downstream suspended sediment-associated and total trace element fluxes increase in the Mississippi and Columbia Basins, whereas fluxes markedly decrease in the Colorado Basin. No consistent pattern in trace element fluxes was detected in the Rio Grande Basin.

Size-fractionation of groundwater arsenic in alluvial aquifers of West Bengal, India: the role of organic and inorganic colloids.

PubMed

Majumder, Santanu; Nath, Bibhash; Sarkar, Simita; Chatterjee, Debashis; Roman-Ross, Gabriela; Hidalgo, Manuela

2014-01-15

Dissolved organic carbon (DOC) and Fe mineral phases are known to influence the mobility of arsenic (As) in groundwater. Arsenic can be associated with colloidal particles containing organic matter and Fe. Currently, no data is available on the dissolved phase/colloidal association of As in groundwater of alluvial aquifers in West Bengal, India. This study investigated the fractional distribution of As (and other metals/metalloids) among the particulate, colloidal and dissolved phases in groundwater to decipher controlling behavior of organic and inorganic colloids on As mobility. The result shows that 83-94% of As remained in the 'truly dissolved' phases (i.e., <0.05 μm size). Strong positive correlation between Fe and As (r(2) between 0.65 and 0.94) is mainly observed in the larger (i.e., >0.05 μm size) colloidal particles, which indicates the close association of As with larger Fe-rich inorganic colloids. In smaller (i.e., <0.05 μm size) colloidal particles strong positive correlation is observed between As and DOC (r(2)=0.85), which highlights the close association of As with smaller organic colloids. As(III) is mainly associated with larger inorganic colloids, whereas, As(V) is associated with smaller organic/organometallic colloids. Scanning Electron Microscopy and Energy Dispersive X-ray spectroscopy confirm the association of As with DOC and Fe mineral phases suggesting the formation of dissolved organo-Fe complexes and colloidal organo-Fe oxide phases. Attenuated total reflectance-Fourier transform infrared spectroscopy further confirms the formation of As-Fe-NOM organometallic colloids, however, a detailed study of these types of colloids in natural waters is necessary to underpin their controlling behavior. © 2013 Elsevier B.V. All rights reserved.

Water-quality assessment of the Rio Grande Valley, Colorado, New Mexico, and Texas; summary and analysis of water-quality data for the basic-fixed-site network, 1993-95

USGS Publications Warehouse

Healy, D.F.

1997-01-01

The Rio Grande Valley study unit of the U.S. Geological Survey National Water-Quality Assessment Program collected monthly water- quality samples at a network of surface-water sites from April 1993 through September 1995. This basic-fixed-site network consisted of nine main-stem sites on the Rio Grande, five sites on tributaries of the Rio Grande, two sites on streams in the Rio Grande Valley study unit that are not directly tributary to the Rio Grande, and one site on a conveyance channel. During each monthly sampling, field properties were measured and samples were collected for the analysis of dissolved solids, major constituents, nutrients, selected trace elements, and suspended-sediment concentrations. During selected samplings, supplemental samples were collected for the analysis of additional trace elements, organic carbon, and/or pesticides. Spatial variations of dissolved-solids, major-constituent, and nutrient data were analyzed. The report presents summary statistics for the monthly water-quality data by sampling site and background information on the drainage basin upstream from each site. Regression equations are presented that relate dissolved-solids, major-constituent, and nutrient concentrations to streamflow, selected field properties, and time. Median instantaneous streamflow at each basic-fixed site ranged from 1.4 to 1,380 cubic feet per second. Median specific conductance at each basic-fixed site ranged from 84 to 1,680 microsiemens per centimeter at 25 degrees Celsius, and median pH values ranged from 7.8 to 8.5. The water sampled at the basic-fixed sites generally was well oxygenated and had a median dissolved-oxygen percent of saturation range from 89 to 108. With the exception of Rio Grande above mouth of Trinchera Creek, near Lasauses, Colorado, dissolved-solids concentrations in the main stem of the Rio Grande generally increased in a downstream direction. This increase is from natural sources such as ground-water inflow and evapotranspiration and from anthropogenic sources such as irrigation- return flows, urban runoff, and wastewater-treatment plant discharges. The smallest median dissolved-solids concentration detected at a basic- fixed site was 58 milligrams per liter and the largest was 1,240 milligrams per liter. The spatial distribution of calcium, magnesium, sodium, sulfate, chloride, and fluoride was similar to the spatial distribution of dissolved solids. The spatial distribution of potassium and bicarbonate varied slightly from that of dissolved solids. Median silica concentrations generally decreased in a downstream direction. Of all cations, calcium and sodium had the largest concentrations at most basic-fixed sites. Bicarbonate and sulfate were the anions having the largest concentrations at most sites. The largest median silica concentration was at Rito de los Frijoles in Bandelier National Monument, New Mexico, where silica composed approximately 50 percent of the dissolved solids. The largest concentrations and largest median concentrations of dissolved-nutrient analytes were detected at Santa Fe River above Cochiti Lake, New Mexico, and Rio Grande at Isleta, New Mexico. The relatively large dissolved-nutrient concentrations at these sites probably were due to discharges from wastewater-treatment plants and urban runoff. The largest concentrations and largest median concentrations of total ammonia plus organic nitrogen and total phosphorus were detected at Rio Puerco near Bernardo, New Mexico. The largest concentrations of these nutrients at this site were associated with runoff from summer thunderstorms. Dissolved-iron concentrations ranged from censored concentrations to 914 micrograms per liter. Median dissolved-iron concentrations ranged from 3 to 160 micrograms per liter. Dissolved-manganese concentrations ranged from censored concent

Effects of Metals Associated with Wildfire Ash on Water Quality

NASA Astrophysics Data System (ADS)

Cerrato, J.; Clark, A.; Correa, N.; Ali, A.; Blake, J.; Bixby, R.

2015-12-01

The forests of the western United States are impacted dramatically by climate change and have suffered from large-scale increases in wildfire activity. This rise in wildfires introduces additional ash to ecosystems and can represent a serious and ongoing threat to water quality in streams and rivers from storm event runoff in burn areas. The effect of metals associated with wildfire ash (from wood collected from the Valles Caldera National Preserve, Jemez Mountains, New Mexico) on solution pH and dissolved oxygen was assessed through a series of laboratory experiments. Microscopy and spectroscopy analyses were conducted to characterize the elemental content and oxidation state of metals in unreacted and reacted ash. Certain metals (e.g., Ca, K, Al, Mg) were detected in ash from ponderosa pine, one of the dominant species in the Valles Caldera, with mean concentrations ranging from 400-1750 mg kg-1. Other metals (e.g., Na, Fe, Mn, V, Zn, Ni) were present at lower mean concentrations ranging from 12-210 mg kg-1. The initial pH after conducting batch experiments reacting ash with water started at 9.9 and the alkalinity of the water was 110 mg L-1 as CaCO3. Solution pH decreased to 8.0 after 48 hours of reaction, which is almost a delta of two pH units. Dissolved oxygen concentrations decreased by 2 mg L-1 over the course of 12 hours before the rate of reaeration surpassed the rate of consumption. This presentation will discuss how redox-active metals, such as Fe and Mn, could contribute to the increased dissolved oxygen demand and fluctuation of the oxidation/reduction potential in the system.

Factors Influencing the Diversity of Iron Uptake Systems in Aquatic Microorganisms

PubMed Central

Desai, Dhwani K.; Desai, Falguni D.; LaRoche, Julie

2012-01-01

Iron (Fe) is an essential micronutrient for many processes in all living cells. Dissolved Fe (dFe) concentrations in the ocean are of the order of a few nM, and Fe is often a factor limiting primary production. Bioavailability of Fe in aquatic environments is believed to be primarily controlled through chelation by Fe-binding ligands. Marine microbes have evolved different mechanisms to cope with the scarcity of bioavailable dFe. Gradients in dFe concentrations and diversity of the Fe-ligand pool from coastal to open ocean waters have presumably imposed selection pressures that should be reflected in the genomes of microbial communities inhabiting the pelagic realm. We applied a hidden Markov model (HMM)-based search for proteins related to cellular iron metabolism, and in particular those involved in Fe uptake mechanisms in 164 microbial genomes belonging to diverse taxa and occupying different aquatic niches. A multivariate statistical approach demonstrated that in phototrophic organisms, there is a clear influence of the ecological niche on the diversity of Fe uptake systems. Extending the analyses to the metagenome database from the Global Ocean Sampling expedition, we demonstrated that the Fe uptake and homeostasis mechanisms differed significantly across marine niches defined by temperatures and dFe concentrations, and that this difference was linked to the distribution of microbial taxa in these niches. Using the dN/dS ratios (which signify the rate of non-synonymous mutations) of the nucleotide sequences, we identified that genes encoding for TonB, Ferritin, Ferric reductase, IdiA, ZupT, and Fe2+ transport proteins FeoA and FeoB were evolving at a faster rate (positive selection pressure) while genes encoding ferrisiderophore, heme and Vitamin B12 uptake systems, siderophore biosynthesis, and IsiA and IsiB were under purifying selection pressure (evolving slowly). PMID:23087680

Vertical variability of arsenic concentrations under the control of iron-sulfur-arsenic interactions in reducing aquifer systems

NASA Astrophysics Data System (ADS)

Pi, Kunfu; Wang, Yanxin; Postma, Dieke; Ma, Teng; Su, Chunli; Xie, Xianjun

2018-06-01

High spatial variability of arsenic (As) concentration in geogenic As-contaminated groundwater has been commonly observed worldwide, but the underlying reasons remain not well understood. Selecting a sulfate-containing, As-affected aquifer at the Datong Basin, northern China as the study area and combining hydrogeochemical investigation and sediment extraction with reactive transport modeling, this work elucidated the roles of Fe-S-As interactions in regulating the vertical variation of As concentration in the groundwater. Dissolved As concentration varied between 0.05 and 18 μmol/L, but generally increased in the depth of 20-25 m and then decreased in 25-30 m. The high-As groundwater contained low Fe(II) (<0.007 mmol/L) and up to 15 μmol/L sulfide, in contrary to the S/SE Asian deltas/floodplains where high Fe(II) and As jointly occur in the groundwater devoid of sulfate reduction. The reductive dissolution of As-bearing Fe(III) oxides coupled to the degradation of organic matter with an estimated maximum rate of 0.22 mmol C/L/yr, mainly accounted for the depth-dependent increase of As concentration in the upper part of the shallow aquifer (<25 m deep). However, the decreasing reactivity of Fe(III) oxides together with the increase of pH over depth rendered the majority of electrons being transferred to sulfate reduction. The Fe(II) sulfides formed as a consequence not only helped to restrict the build-up of Fe(II) in the groundwater but also probably co-precipitated As to prompt As decrease in the depth of 25-30 m. Arsenite adsorbed on remaining Fe(III) oxides and newly-formed Fe(II) sulfides is another important pool of As in the aquifer, which varies in response to the extents of Fe(III)-oxide and sulfate reduction and consequently alters As distribution coefficient between the solid and the aqueous phases. This study highlights the importance of coupled geochemical cycling of Fe, S and As for As mobilization and reveals how it regulates As partitioning between groundwater and sediments.

Metal concentrations in water and sediments from tourist beaches of Acapulco, Mexico.

PubMed

Jonathan, M P; Roy, P D; Thangadurai, N; Srinivasalu, S; Rodríguez-Espinosa, P F; Sarkar, S K; Lakshumanan, C; Navarrete-López, M; Muñoz-Sevilla, N P

2011-04-01

A survey on the metal concentrations (As, Ba, Cd, Co, Cr, Cu, Fe, Mn, Ni, Pb, Sr, V, Zn) in beach water and sediments is reported from the tourist destination of Acapulco city on the Pacific coast of Mexico. The concentration of dissolved trace metals (DTMs) in beach water and acid leachable trace metals (ALTMs) in sediments indicated that they are anthropogenic in nature due to the increased tourist activities in the crowded beach locations. The statistical analysis indicates Fe and Mn play a major role as metal scavengers in both the medium (water and sediment) and the higher value of other metals is site specific in the study area, indicating that they are transported from the local area. Comparison results suggest that the beach water quality has deteriorated more than the sediments and special care needs to be taken to restore the beach quality. Copyright © 2011 Elsevier Ltd. All rights reserved.

Sulfide oxidation and distribution of metals near abandoned copper mines in coastal environments, Prince William Sound, Alaska, USA

USGS Publications Warehouse

Koski, R.A.; Munk, L.; Foster, A.L.; Shanks, Wayne C.; Stillings, L.L.

2008-01-01

The oxidation of sulfide-rich rocks, mostly leftover debris from Cu mining in the early 20th century, is contributing to metal contamination of local coastal environments in Prince William Sound, Alaska. Analyses of sulfide, water, sediment, precipitate and biological samples from the Beatson, Ellamar, and Threeman mine sites show that acidic surface waters generated from sulfide weathering are pathways for redistribution of environmentally important elements into and beyond the intertidal zone at each site. Volcanogenic massive sulfide deposits composed of pyrrhotite and (or) pyrite + chalcopyrite + sphalerite with subordinate galena, arsenopyrite, and cobaltite represent potent sources of Cu, Zn, Pb, As, Co, Cd, and Hg. The resistance to oxidation among the major sulfides increases in the order pyrrhotite ??? sphalerite < chalcopyrite ??? pyrite; thus, pyrrhotite-rich rocks are typically more oxidized than those dominated by pyrite. The pervasive alteration of pyrrhotite begins with rim replacement by marcasite followed by replacement of the core by sulfur, Fe sulfate, and Fe-Al sulfate. The oxidation of chalcopyrite and pyrite involves an encroachment by colloform Fe oxyhydroxides at grain margins and along crosscutting cracks that gradually consumes the entire grain. The complete oxidation of sulfide-rich samples results in a porous aggregate of goethite, lepidocrocite and amorphous Fe-oxyhydroxide enclosing hydrothermal and sedimentary silicates. An inverse correlation between pH and metal concentrations is evident in water data from all three sites. Among all waters sampled, pore waters from Ellamar beach gravels have the lowest pH (???3) and highest concentrations of base metals (to ???25,000 ??g/L), which result from oxidation of abundant sulfide-rich debris in the sediment. High levels of dissolved Hg (to 4100 ng/L) in the pore waters probably result from oxidation of sphalerite-rich rocks. The low-pH and high concentrations of dissolved Fe, Al, and SO4 are conducive to precipitation of interstitial jarosite in the intertidal gravels. Although pore waters from the intertidal zone at the Threeman mine site have circumneutral pH values, small amounts of dissolved Fe2+ in the pore waters are oxidized during mixing with seawater, resulting in precipitation of Fe-oxyhydroxide flocs along the beach-seawater interface. At the Beatson site, surface waters funneled through the underground mine workings and discharged across the waste dumps have near-neutral pH (6.7-7.3) and a relatively small base-metal load; however, these streams probably play a role in the physical transport of metalliferous particulates into intertidal and offshore areas during storm events. Somewhat more acidic fluids, to pH 5.3, occur in stagnant seeps and small streams emerging from the Beatson waste dumps. Amorphous Fe precipitates in stagnant waters at Beatson have high Cu (5.2 wt%) and Zn (2.3 wt%) concentrations that probably reflect adsorption onto the extremely high surface area of colloidal particles. Conversely, crystalline precipitates composed of ferrihydrite and schwertmannite that formed in the active flow of small streams have lower metal contents, which are attributed to their smaller surface area and, therefore, fewer reactive sorption sites. Seeps containing precipitates with high metal contents may contribute contaminants to the marine environment during storm-induced periods of high runoff. Preliminary chemical data for mussels (Mytilus edulis) collected from Beatson, Ellamar, and Threeman indicate that bioaccumulation of base metals is occurring in the marine environment at all three sites.

Metal-fluxes characterization at a catchment scale: Study of mixing processes and end-member analysis in the Meca River watershed (SW Spain)

NASA Astrophysics Data System (ADS)

Cánovas, C. R.; Macías, F.; Olías, M.; López, R. Pérez; Nieto, J. M.

2017-07-01

Fluxes of acidity and contaminants from acid mine drainage (AMD) sources to the receiving surface water bodies were studied in a mining-impacted watershed (Meca River, SW Spain) using a novel methodology based on the joint application of EMMA and MIX codes. The application of EMMA and elemental ratios allowed delimiting the end-members responsible for water quality variations at a catchment scale. The further application of MIX quantified the significant impact of AMD on the river quality; less than 10% of AMD relative contribution is enough to maintain acidic conditions during most of the year. The mixing model also provided information about the element mobility, distinguishing those elements with a quasi-conservative behavior (e.g., Cu, Zn, Al, Co or Ni) from those affected by mineral precipitation/dissolution (e.g., K, Si, Na, Sr, Ca, Fe, Pb, or As). Floods are the main driver of dissolved and, mainly particulate, contaminants in the catchment. Thus, the first rainfall events in November only accounted for 19% of the annual Meca flow but yielded between 26 and 43% of the net acidity and dissolved metal loads (mainly, Fe, As and Pb). Concerning particulate transport, around 332 tons of particulate Fe, 49 tons of Al, 0.79 tons of As and 0.37 tons of Pb were recorded during these first floods. The particulate As concentration can be up to 34 times higher than the dissolved one during floods and between 2 and 4 times higher for Fe, Pb and Cr. This integrated modeling approach could be a promising and useful tool to face future restoration plans in derelict mines worldwide. This approach would allow prioritizing remedial measures, achieving an environmental and cost-effective restoration of degraded areas.

Impact of ocean acidification on phytoplankton assemblage, growth, and DMS production following Fe-dust additions in the NE Pacific high-nutrient, low-chlorophyll waters

NASA Astrophysics Data System (ADS)

Mélançon, Josiane; Levasseur, Maurice; Lizotte, Martine; Scarratt, Michael; Tremblay, Jean-Éric; Tortell, Philippe; Yang, Gui-Peng; Shi, Guang-Yu; Gao, Huiwang; Semeniuk, David; Robert, Marie; Arychuk, Michael; Johnson, Keith; Sutherland, Nes; Davelaar, Marty; Nemcek, Nina; Peña, Angelica; Richardson, Wendy

2016-03-01

Ocean acidification (OA) is likely to have an effect on the fertilizing potential of desert dust in high-nutrient, low-chlorophyll oceanic regions, either by modifying iron (Fe) speciation and bioavailability or by altering phytoplankton Fe requirements and acquisition. To address this issue, short incubations (4 days) of northeast subarctic Pacific waters enriched with either FeSO4 or dust and set at pH 8.0 (in situ) and 7.8 were conducted in August 2010. We assessed the impact of a decrease in pH on dissolved Fe concentration, phytoplankton biomass, taxonomy and productivity, and the production of dimethylsulfide (DMS) and its algal precursor dimethylsulfoniopropionate (DMSP). Chlorophyll a (chl a) remained unchanged in the controls and doubled in both the FeSO4-enriched and dust-enriched incubations, confirming the Fe-limited status of the plankton assemblage during the experiment. In the acidified treatments, a significant reduction (by 16-38 %) in the final concentration of chl a was measured compared to their nonacidified counterparts, and a 15 % reduction in particulate organic carbon (POC) concentration was measured in the dust-enriched acidified treatment compared to the dust-enriched nonacidified treatment. FeSO4 and dust additions had a fertilizing effect mainly on diatoms and cyanobacteria as estimated from algal pigment signatures. Lowering the pH affected mostly the haptophytes, but pelagophyte concentrations were also reduced in some acidified treatments. Acidification did not significantly alter DMSP and DMS concentrations. These results show that dust deposition events in a low-pH iron-limited northeast subarctic Pacific are likely to stimulate phytoplankton growth to a lesser extent than in today's ocean during the few days following fertilization and point to a low initial sensitivity of the DMSP and DMS dynamics to OA.

Eruptive Dynamics Inferred from Textural Analysis of Ash Time Series: The 2015 Reawakening of Cotopaxi Volcano

NASA Astrophysics Data System (ADS)

Gaunt, H. E.; Bernard, B.; Hidalgo, S.; Proaño, A.; Wright, H. M. N.; Mothes, P. A.; Criollo, E.

2016-12-01

The eruptive process that took place in October 2011 in the submarine volcano Tagoro off the Island of El Hierro (Canary Island) and the subsequent degasification stage, five months later, have increased the concentration of TdFe(II) (Total dissolved iron(II)) in the waters nearest to the volcanic edifice. In order to detect any variation in concentrations of TdFe(II) due to hydrothermal emissions, three cruises were carried out two years after the eruptive process in October 2013, March 2014, May 2015, March 2016 and November 2016. The results from these cruises confirmed important positive anomalies in TdFe(II), which coincided with negatives anomalies in pHF,is (pH in free scale, at in situ conditions) located in the proximity of the main cone. Maximum values in TdFe(II) both at the surface, associated to chlorophyll a maximum, and at the sea bottom, were also observed, showing the important influence of organic complexation and particle re-suspension processes. Temporal variability studies were carried out over periods ranging from hours to days in the stations located over the main and two secondary cones in the volcanic edifice with positive anomalies in TdFe(II) concentrations and negative anomalies in pHF,is values. Observations showed an important variability in both pHF,is and TdFe(II) concentrations, which indicated the volcanic area was affected by a degasification process that remained in the volcano after the eruptive phase had ceased. Fe(II) oxidation kinetic studies were also undertaken in order to analyze the effects of the seawater properties in the proximities of the volcano on the oxidation rate constants and t1/2 (half-life time) of ferrous iron. The increased TdFe(II) concentrations and the low associated pHF,is values acted as an important fertilization event in the seawater around the Tagoro volcano at the Island of El Hierro providing optimal conditions for the regeneration of the area.

Identification of an Archean marine oxygen oasis

DOE Office of Scientific and Technical Information (OSTI.GOV)

Riding, Dr Robert E; Fralick, Dr Philip; Liang, Liyuan

2014-01-01

The early Earth was essentially anoxic. A number of indicators suggest the presence of oxygenic photosynthesis 2700 3000 million years (Ma) ago, but direct evidence for molecular oxygen (O2) in seawater has remained elusive. Here we report rare earth element (REE) analyses of 2800 million year old shallowmarine limestones and deep-water iron-rich sediments at Steep Rock Lake, Canada. These show that the seawater from which extensive shallow-water limestones precipitated was oxygenated, whereas the adjacent deeper waters where iron-rich sediments formed were not. We propose that oxygen promoted limestone precipitation by oxidative removal of dissolved ferrous iron species, Fe(II), to insolublemore » Fe(III) oxyhydroxide, and estimate that at least 10.25 M oxygen concentration in seawater was required to accomplish this at Steep Rock. This agrees with the hypothesis that an ample supply of dissolved Fe(II) in Archean oceans would have hindered limestone formation. There is no direct evidence for the oxygen source at Steep Rock, but organic carbon isotope values and diverse stromatolites in the limestones suggest the presence of cyanobacteria. Our findings support the view that during the Archean significant oxygen levels first developed in protected nutrient-rich shallow marine habitats. They indicate that these environments were spatially restricted, transient, and promoted limestone precipitation. If Archean marine limestones in general reflect localized oxygenic removal of dissolved iron at the margins of otherwise anoxic iron-rich seas, then early oxygen oases are less elusive than has been assumed.« less

Bacterial Fe(II) oxidation distinguished by long-range correlation in redox potential

NASA Astrophysics Data System (ADS)

Enright, Allison M. L.; Ferris, F. Grant

2016-05-01

The kinetics of bacterial Fe(II) oxidation was investigated 297 m underground at the Äspö Hard Rock Laboratory (near Oskarshamn, Sweden) under steady state groundwater flow conditions in a flow-through cell containing well-developed flocculent mats of bacteriogenic iron oxides (BIOS). Pseudo first-order rate constants of 0.004 min-1 and 0.009 min-1 were obtained for chemical and bacterial Fe(II) oxidation, respectively, based on the 104 min retention time of groundwater in the flow cell, inlet Fe(II) concentration of 21.0 ± 0.5 µm, outlet Fe(II) concentration of 8.5 ± 0.7 µm, as well as constant pH = - log H+ of 7.42 ± 0.01, dissolved O2 concentration of 0.11 ± 0.01 mg/L, and groundwater temperature of 12.4 ± 0.1°C. Redox potential was lower at the BIOS-free inlet (-135.4 ± 1.16 mV) compared to inside BIOS within the flow cell (-112.6 ± 1.91 mV), consistent with the Nernst relationship and oxidation of Fe(II) to Fe(III). Further evaluation of the redox potential time series data using detrended fluctuation analysis (DFA) revealed power law scaling in the amplitude of fluctuations over increasing intervals of time with significantly different (p < 0.01) DFA α scaling exponents of 1.89 ± 0.03 for BIOS and 1.67 ± 0.06 at the inlet. These α values not only signal the presence of long-range correlation in the redox potential time series measurements but also distinguish between the slower rate of chemical Fe(II) oxidation at the inlet and faster rate accelerated by FeOB in BIOS.

Effect of flood events on transport of suspended sediments, organic matter and particulate metals in a forest watershed in the Basque Country (Northern Spain).

PubMed

Peraza-Castro, M; Sauvage, S; Sánchez-Pérez, J M; Ruiz-Romera, E

2016-11-01

An understanding of the processes controlling sediment, organic matter and metal export is critical to assessing and anticipating risk situations in water systems. Concentrations of suspended particulate matter (SPM), dissolved (DOC) and particulate (POC) organic carbon and metals (Cu, Ni, Pb, Cr, Zn, Mn, Fe) in dissolved and particulate phases were monitored in a forest watershed in the Basque Country (Northern Spain) (31.5km(2)) over three hydrological years (2009-2012), to evaluate the effect of flood events on the transport of these materials. Good regression was found between SPM and particulate metal concentration, making it possible to compute the load during the twenty five flood events that occurred during the study period at an annual scale. Particulate metals were exported in the following order: Fe>Mn>Zn>Cr>Pb>Cu>Ni. Annual mean loads of SPM, DOC and POC were estimated at 2267t, 104t and 57t, respectively, and the load (kg) of particulate metals at 76 (Ni), 83 (Cu), 135 (Pb), 256 (Cr), 532 (Zn), 1783 (Mn) and 95170 (Fe). Flood events constituted 91%-SPM, 65%-DOC, 71%-POC, 80%-Cu, 85%-Ni, 72%-Pb, 84%-Cr, 74%-Zn, 87%-Mn and 88%-Fe of total load exported during the three years studied. Flood events were classified into three categories according to their capacity for transporting organic carbon and particulate metals. High intensity flood events are those with high transport capacity of SPM, organic carbon and particulate metals. Most of the SPM, DOC, POC and particulate metal load was exported by this type of flood event, which contributed 59% of SPM, 45% of organic carbon and 54% of metals. Copyright © 2016 Elsevier B.V. All rights reserved.

Inhibition of hydroxyl radical reaction with aromatics by dissolved natural organic matter

USGS Publications Warehouse

Lindsey, M.E.; Tarr, M.A.

2000-01-01

Reaction of aromatic compounds with hydroxyl radical is inhibited by dissolved natural organic matter (NOM). The degree of inhibition is significantly greater than that expected based on a simple model in which aromatic compound molecules bound to NOM are considered to be unreactive. In this study, hydroxyl radical was produced at steady-state concentrations using Fenton chemistry (H2O2 + Fe2+ ??? Fe3+ + HO- + HO??). Suwannee River fulvic acid and humic acid were used as NOM. The most likely mechanism for the observed inhibition is that hydroxyl radical formation occurs in microenvironmental sites remote from the aromatic compounds. In addition to changes in kinetics, pyrene hydroxyl radical reaction also exhibited a mechanistic change in the presence of fulvic acid. The mechanism changed from a reaction that was apparently firstorder in pyrene to one that was apparently secondorder in pyrene, indicating that pyrene self-reaction may have become the dominant mechanism in the presence of fulvic acid. Dissolved NOM causes significant changes in the rate and mechanism of hydroxyl radical degradation of aromatic compounds. Consequently, literature rate constants measured in pure water will not be useful for predicting the degradation of pollutants in environmental systems. The kinetic and mechanistic information in this study will be useful for developing improved degradation methods involving Fenton chemistry.Reaction of aromatic compounds with hydroxyl radical is inhibited by dissolved natural organic matter (NOM). The degree of inhibition is significantly greater than that expected based on a simple model in which aromatic compounds molecules bounds to NOM are considered to be unreactive. In this study, hydroxyl radical was produced at steady-state concentrations using Fenton chemistry (H2O2 + Fe2+ ??? Fe3+ + HO- + HO??). Suwannee River fulvic acid and humic acid were used as NOM. The most likely mechanisms for the observed inhibition is that hydroxyl radical formation occurs in microenvironmental sites remote from the aromatic compounds. In addition to changes in kinetics, pyrene hydroxyl radical reaction also exhibited a mechanistic change in the presence of fulvic acid. The mechanism changed from a reaction that was apparently first-order in pyrene to one that was apparently second-order in pyrene, indicating that pyrene self-reaction may have become the dominant mechanism in the presence of fulvic acid. Dissolved NOM causes significant changes in the rate and mechanism of hydroxyl radical degradation of aromatic compounds. Consequently, literature rate constants measured in pure water will not be useful for predicting the degradation of pollutants in environmental systems. The kinetic and mechanistic information in this study will be useful for developing improved degradation methods involving Fenton chemistry.

Sulfide Melts and Chalcophile Element Behavior in High Temperature Systems

NASA Astrophysics Data System (ADS)

Wood, B. J.; Kiseeva, K.

2016-12-01

We recently found that partition coefficients (Di) of many weakly and moderately chalcophile elements (e.g., Cd, Zn, Co, Cr, Pb, Sb, In) between sulfide and silicate melts are simple functions of the FeO content of the silicate liquid: logDi A-Blog[FeO] where [FeO] is the FeO concentration in the silicate, A and B are constants and the latter is related to the valency of the element of interest. In contrast, some strongly chalcophile (e.g Cu, Ni, Ag) and lithophile elements (e.g Mn) show marked deviations from linearity on a plot of logDi vs log[FeO]. More recent experiments show that linear behavior is confined to elements whose affinities for S and O are similar to those of Fe. In the case of elements more strongly lithophile than Fe (Ti, U, REE, Zr, Nb, Ta, Mn) a plot of logDi versus log[FeO] describes a U-shape with the element partitioning strongly into the sulfide at very low FeO and again at very high FeO content of the silicate melt. In contrast, strongly chalcophile elements (Cu, Ni, Ag) describe an n-shape on the plot of logD vs log[FeO]. The result is that lithophile elements such as Nb become more "chalcophile" than Cu at very low and very high FeO contents of the silicate melt. The reasons for this surprising behavior are firstly that, at very low FeO contents the silicate melt dissolves substantial amounts of sulfur, which drives down the activity of FeO and, from mass-action "pulls" the lihophile element into the sulfide. At high FeO contents of the silicate the sulfide itself starts to dissolve substantial amounts of oxygen and lithophile elements follow the oxygen into the sulfide. Given the principles which we have established, we are able to describe the patterns of chalcophile element behavior during partial melting and fractional crystallisation on Earth and also on bodies such as Mercury and Mars which are, respectively, strongly reduced relative to Earth and more oxidised than Earth.

Attenuation and colloidal mobilization of bacteriophages in natural sediments under anoxic as compared to oxic conditions.

PubMed

Klitzke, Sondra; Schroeder, Jendrik; Selinka, Hans-Christoph; Szewzyk, Regine; Chorus, Ingrid

2015-06-15

Redox conditions are known to affect the fate of viruses in porous media. Several studies report the relevance of colloid-facilitated virus transport in the subsurface, but detailed studies on the effect of anoxic conditions on virus retention in natural sediments are still missing. Therefore, we investigated the fate of viruses in natural flood plain sediments with different sesquioxide contents under anoxic conditions by considering sorption to the solid phase, sorption to mobilized colloids, and inactivation in the aqueous phase. Batch experiments were conducted under oxic and anoxic conditions at pH values between 5.1 and 7.6, using bacteriophages MS2 and PhiX174 as model viruses. In addition to free and colloid-associated bacteriophages, dissolved and colloidal concentrations of Fe, Al and organic C as well as dissolved Ca were determined. Results showed that regardless of redox conditions, bacteriophages did not adsorb to mobilized colloids, even under favourable charge conditions. Under anoxic conditions, attenuation of bacteriophages was dominated by sorption over inactivation, with MS2 showing a higher degree of sorption than PhiX174. Inactivation in water was low under anoxic conditions for both bacteriophages with about one log10 decrease in concentration during 16 h. Increased Fe/Al concentrations and a low organic carbon content of the sediment led to enhanced bacteriophage removal under anoxic conditions. However, even in the presence of sufficient Fe/A-(hydr)oxides on the solid phase, bacteriophage sorption was low. We presume that organic matter may limit the potential retention of sesquioxides in anoxic sediments and should thus be considered for the risk assessment of virus breakthrough in the subsurface. Copyright © 2015 Elsevier B.V. All rights reserved.

Tidally driven pore water exchange in offshore intertidal sandbanks: Part I. Field measurements

NASA Astrophysics Data System (ADS)

Gibbes, B.; Robinson, C.; Carey, H.; Li, L.; Lockington, D.

2008-08-01

In recent years blooms of the toxic marine cyanobacteria Lyngbya majuscula have been frequently observed in a system of offshore intertidal sandbanks in Moreton Bay, Australia. Past research suggests that these blooms are linked to the presence of bio-available forms of iron. Using hydraulic and pore water chemistry data collected from a shore normal transect at an offshore bloom site, the role of tidally driven exchange as a potential mechanism for delivery of bio-available iron across the sediment-water interface was examined. Field data revealed a residual pore water flow system in the sandbank, with seawater entering the upper sandbank platform and discharging through the bank edge. Upward flow and elevated near-surface dissolved Fe(II) concentrations (>20 μM Fe(II) at -0.05 m depth) were measured simultaneously in the discharge zones at the sandbank edge. The measured concentrations were more than four times greater than concentrations previously shown to stimulate L. majuscula growth. These results suggest that the tidally driven exchange mechanism might be capable of delivering dissolved Fe(II) to sites within offshore intertidal sandbanks where blooms of L. majuscula have been observed. While the source of the iron was not identified, potential candidates are discussed. These findings have implications for the current conceptual model for L. majuscula blooms in offshore intertidal sandbanks within Moreton Bay. Further investigations are required to fully understand the role of tidally driven exchange in controlling the export of bio-available iron to coastal waters at the field site. In particular there is a need to better assess the link between the pore water flows and the geochemical reactions that might occur along the flow path.

Biogeochemical Activity of Siderophilic Cyanobacteria and Insights from their Genomes Implications for the Development of New Biosignatures

NASA Technical Reports Server (NTRS)

Brown, I. I.; Bryant, D. A.; Thomas,-Keprta, K. L.; Tringe, S. G.; Sarkisova, S. A.; Galindo, C., Jr.; Malley, K.; Sosa, O.; Garrison, D. H.; McKay, David S.

2010-01-01

Verifying the links between genomie features in living organisms and their mineralization/demineralization activity will help to reveal traces of life on Earth and beyond. Among contemporary environments, iron-depositing hot springs (IDHS) may represent one of the most appropriate natural models for insights into ancient life since organisms may have originated on Earth and possibly Mars in association with hydrothennal activity and high [Fe(2+)]. Siderophilic or "iron-loving" cyanobacteria (CB) inhabiting IDHS may have genomic features and properties similar to those of ancient organisms because abundant Fe(2+) in IDHS has a strong potential to increase the magnitude of oxidative stress. That is why specific and/or additional proteins involved in Fe mineralization by siderophilic CB are expected. Inorganic polyphosphates (PPi) are known to increase the viability of prokaryotes Linder heavy metal concentrations and UV stress conditions. PPi have also been proposed as biosignatures. Ancient CB could have also been stressed by occasional migrations from the Fe(2+) rich Ocean to the basaltic land which was almost devoid of dissolved Fe(2+). Thus, the study of the adaptation reactions of siderophilic CB to fluctuation of dissolved Fe level may shed light on the paleophysiology of ancient oxygenic prokaryotes. Moreover, bioweathered Fe, Al, P, Cu, Ti and rare earth elements can be thought of as candidate organomarkers that document the effects of or ganic molecules in weathered rocks. However, the molecular mechanisms of the maintenance of Fe homeostasis in siderophilic CB, the role of PPi for this process and bioweathering activities are poorly understood. Here we present preliminary results describing a new mechanism of Fe mineralization in siderophilic CB, the effect of Fe on the generation of PPi bodies in siderophilic CB, their bioweathering activity and preliminary analysis of the diversity of proteins involved in the prevention of oxidative stress in phototrophs inhabiting IDHS.

Contrasted response of colloidal, organic and inorganic dissolved phosphorus forms during rewetting of dried riparian soils

NASA Astrophysics Data System (ADS)

Gu, Sen; Gruau, Gérard; Malique, François; Dupas, Rémi; Gascuel-Odoux, Chantal; Petitjean, Patrice; Bouhnik-Le Coz, Martine

2017-04-01

Riparian vegetated buffer strip (RVBS) are currently used to protect surface waters from phosphorus (P) emissions because of their ability to retain P-enriched soil particles. However, this protection role may be counterbalanced by the development in these zones of conditions able to trigger the release of highly mobile dissolved or colloidal P forms. Rewetting after drying is one of these conditions. So far, the potential sources of P mobilized during rewetting after drying are not clearly identified, nor are clearly identified the chemical nature of the released dissolved P species, or the role of the soil P speciation on these forms. In this study, two riparian soils (G and K) showing contrasting soil P speciation (65% of inorganic P species in soil G, as against 70% of organic P) were submitted to three successive dry/wet cycles in the laboratory. Conventional colorimetric determination of P concentrations combined with ultrafiltration, and measurements of iron (Fe) and aluminum (Al) and dissolved organic carbon (DOC) contents using ICP-MS and TOC analyzers, respectively, were used to study the response of the different P forms to rewetting after drying and also their release kinetics during soil leaching. For both soils, marked P release peaks were observed at the beginning of each wet cycles, with the organic-rich K soils giving, however, larger peaks than the inorganic one (G soil). For both soils also, concentrations in molybdate reactive P (MRP) remained quite constant throughout each leaching episode, contrary to the molybdate unreactive P (MUP) concentrations which were high immediately after rewetting and then decreased rapidly during leaching. A speciation change was observed from the beginning to the end of all leaching cycles. Colloidal P was found to be a major fraction of the total P immediately after rewetting (up to 50-70%) and then decreased to the end of each wet cycle where most of the eluted P was true dissolved inorganic P. Colloidal-P exhaustion was tightly associated with DOC, Fe and Al exhaustions. Colloids were larger in size at the beginning than at the end of all cycles. Peak at the beginning of each wet cycles remained quite constant even after two drying/leaching cycles, evidencing the existence of mechanisms able to rebuild a pool of leachable P during drying process. Thus, there was clearly a control of soil characteristics on the released P forms in leachates. Colloidal P carriers appeared to consist of Fe and/or Al oxyhydroxide nano/microparticles associated with organic matter. Most importantly, a survey of colloidal size distribution during leaching indicated that the rapidly exhausted MUP pool consisted of larger size MUP and colloidal P phases, which probably originated from soil macropores, while the relatively infinite MRP pool consisted of smaller size colloidal P and true dissolved MRP phases, which was mobilized from soil micropores. These results further demonstrate the ability of rewetting after drying to lead to pulses of dissolved and colloidal P in riparian soils, thereby evidencing the risks that P-enriched soil particles accumulated in RVBS could constitute a long-term threat for surface water.

Hydrothermal sediments are a source of water column Fe and Mn in the Bransfield Strait, Antarctica

NASA Astrophysics Data System (ADS)

Aquilina, Alfred; Homoky, William B.; Hawkes, Jeffrey A.; Lyons, Timothy W.; Mills, Rachel A.

2014-07-01

Short sediment cores were collected from ∼1100 m water depth at the top of Hook Ridge, a submarine volcanic edifice in the Central Basin of the Bransfield Strait, Antarctica, to assess Fe and Mn supply to the water column. Low-temperature hydrothermal fluids advect through these sediments and, in places, subsurface H2S is present at high enough concentrations to support abundant Sclerolinum sp., an infaunal tubeworm that hosts symbiotic thiotrophic bacteria. The water column is fully oxic, and oxygen penetration depths at all sites are 2-5 cmbsf. Pore water Fe and Mn content is high within the subsurface ferruginous zone (max. 565 μmol Fe L-1, >3-7 cmbsf)-14-18 times higher than values measured at a nearby, background site of equivalent water depth. Diffusion and advection of pore waters supply significant Fe and Mn to the surface sediment. Sequential extraction of the sediment demonstrates that there is a significant enrichment in a suite of reactive, authigenic Fe minerals in the upper 0-5 cm of sediment at one site characterised by weathered crusts at the seafloor. At a site with only minor authigenic mineral surface enrichment we infer that leakage of pore water Fe and Mn from the sediment leads to enriched total dissolvable Fe and Mn in bottom waters. An Eh sensor mounted on a towed package mapped a distinct Eh signature above this coring site which is dispersed over several km at the depth of Hook Ridge. We hypothesise that the main mechanism for Fe and Mn efflux from the sediment is breach of the surface oxic layer by the abundant Sclerolinum sp., along with episodic enhancements by physical mixing and resuspension of sediment in this dynamic volcanic environment. We propose that Hook Ridge sediments are an important source of Fe and Mn to the deep waters of the Central Basin in the Bransfield Strait, where concentrations are sustained by the benthic flux, and Fe is stabilised in the water column as either colloidal phases or ligand-bound dissolved species. Entrainment of this water mass into the Drake Passage and thereby the Antarctic Circumpolar Current could provide a significant metal source to this HNLC region of the Southern Ocean if mixing and upwelling occurs before removal of this metal pool to underlying sediments. Sediment-covered volcanic ridges are common within rifted margins and may play a previously overlooked role in the global Fe cycle.

Arsenic Adsorption Equilibrium Concentration and Adsorption Rate of Activated Carbon Coated with Ferric-Aluminum Hydroxides

NASA Astrophysics Data System (ADS)

Zhang, M.; Sugita, H.; Oguma, T.; Hara, J.; Takahashi, S.

2015-12-01

In some areas of developing countries, ground or well water contaminated with arsenic has been reluctantly used as drinking water. It is highly desirable that effective and inexpensive arsenic removal agents should be developed and provided to reduce the potential health risk. Previous studies demonstrated that activated carbon coated with ferric-aluminum hydroxides (Fe-Al-C) has high adsorptive potential for removal of arsenic. In this study, a series of experiments using Fe-Al-C were carried to discuss adsorption equilibrium time, adsorption equilibrium concentration and adsorption rate of arsenic for Fe-Al-C. Fe-Al-C used in this study was provided by Astec Co., Ltd. Powder reagent of disodium hydrogen arsenate heptahydrate was dissolved into ion-exchanged water. The solution was then further diluted with ion-exchanged water to be 1 and 10 mg/L as arsenic concentration. The pH of the solution was adjusted to be around 7 by adding HCl and/or NaOH. The solution was used as artificial arsenic contaminated water in two types of experiments (arsenic adsorption equilibrium and arsenic adsorption rate tests). The results of the arsenic equilibrium tests were showed that a time period of about 3 days to reach apparent adsorption equilibrium for arsenic. The apparent adsorption equilibrium concentration and adsorbed amount of arsenic on Fe-Al-C adsorbent could be estimated by application of various adsorption isotherms, but the distribution coefficient of arsenic between solid and liquid varies with experimental conditions such as initial concentration of arsenic and addition concentration of adsorbent. An adsorption rate equation that takes into account the reduction in the number of effective adsorption sites on the adsorbent caused by the arsenic adsorption reaction was derived based on the data obtained from the arsenic adsorption rate tests.

Influence of Dissolved Organic Matter and Fe (II) on the Abiotic Reduction of Pentachloronitrobenzene

EPA Science Inventory

Nitroaromatic pesticides (NAPs) are hydrophobic contaminants that can accumulate in sediments by the deposition of suspended solids from surface waters. Fe(II) and dissolved organic matter (DOM), present in suboxic and anoxic zones of freshwater sediments, can transform NAPs in n...

The impact of changing surface ocean conditions on the dissolution of aerosol iron

NASA Astrophysics Data System (ADS)

Fishwick, Matthew P.; Sedwick, Peter N.; Lohan, Maeve C.; Worsfold, Paul J.; Buck, Kristen N.; Church, Thomas M.; Ussher, Simon J.

2014-11-01

The proportion of aerosol iron (Fe) that dissolves in seawater varies greatly and is dependent on aerosol composition and the physicochemical conditions of seawater, which may change depending on location or be altered by global environmental change. Aerosol and surface seawater samples were collected in the Sargasso Sea and used to investigate the impact of these changing conditions on aerosol Fe dissolution in seawater. Our data show that seawater temperature, pH, and oxygen concentration, within the range of current and projected future values, had no significant effect on the dissolution of aerosol Fe. However, the source and composition of aerosols had the most significant effect on the aerosol Fe solubility, with the most anthropogenically influenced samples having the highest fractional solubility (up to 3.2%). The impact of ocean warming and acidification on aerosol Fe dissolution is therefore unlikely to be as important as changes in land usage and fossil fuel combustion. Our experimental results also reveal important changes in the size distribution of soluble aerosol Fe in solution, depending on the chemical conditions of seawater. Under typical conditions, the majority (77-100%) of Fe released from aerosols into ambient seawater existed in the colloidal (0.02-0.4 µm) size fraction. However, in the presence of a sufficient concentration of strong Fe-binding organic ligands (10 nM) most of the aerosol-derived colloidal Fe was converted to soluble Fe (<0.02 µm). This finding highlights the potential importance of organic ligands in retaining aerosol Fe in a biologically available form in the surface ocean.

Trace metals in the Ob and Yenisei Rivers' Estuaries (the Kara Sea).

NASA Astrophysics Data System (ADS)

Demina, L. L.

2014-12-01

Behavior of some trace metals (Al, As, Cd, Co, Cr, Cu, Fe, Mn, Ni and Pb) in water column (soluble <0.45 µm and particulate fractions) and bottom sediments (surface and cores) along the two transects from the Ob River and Yenisei River Estuaries to the Kara Sea was studied. The length of both transects was about 700 km. Water depth was 12-63 m, O2 dissolved :5.36-9.55 ml l-1. Along the transects salinity increased from 0.07 to 34.2 psu, while the SPM' concentration decreased from 10.31 to 0.31 mg/l. Total suspended particulate matter load is more than one order of magnitude higher in the Ob River Estuary comparing to that of the Yenisei River. It has led to a significant difference between the suspended trace metals' concentrations (µg/l) in water of the two estuaries. With salinity increase along transects Fe susp., Mn susp. and Zn susp. decreased by a factor of 100-500, that has led to a growth of a relative portion of dissolved trace metals followed by their bioaccumulation (Demina et al., 2010). A strong direct correlation between suspended Cu, Fe and SPM mass concentration was found. For the first time along the Yenisei River' Estuary -the Kara Sea transect a direct positive correlation between Cu suspended and volume concentration of SPM (mg/ml3) was found, that was attributed to contribution of phytoplankton aggregates in the SPM composition. A trend of relationship between content of suspended As and pelitic fraction (2-10 µm) of SPM was firstly found in theses basins also. Study of trace metal speciation in the bottom sediments (adsorbed, associated with Fe-Mn (oxyhydr)oxides, organic matter and fixed in the mineral lattice or refractory) has revealed the refractory fraction to be prevailing (70-95% total content) for Fe, Zn, Cu, Co, Ni, Cr, Cd and Pb. That means that toxic heavy metals were not available for bottom fauna. Mn was predominantly found in the adsorbed and (oxyhydr)oxides geochemically labile forms, reflecting the redox condition change along both transects and within the sedimentary cores. References. Demina L.L., Gordeev V.V., Galkin S.V., Kravchishina M.D. Biogeochemistry of some heavy metals and metalloids along the transect the Ob River Estuary - the Kara Sea. Oceanology, 2010, vo. 50, No 5, pp. 729- 742.

Effects of Hydrothermal Scavenging of 230Th in the Eastern Equatorial Pacific Translated to the Deep Waters of the Central Equatorial Pacific

NASA Astrophysics Data System (ADS)

Lopez, G. I.; Marcantonio, F.

2014-12-01

Although we were not involved in the 2013 US GEOTRACES zonal transect in the eastern tropical south Pacific, our results in the central tropical Pacific are complementary in that they shed light on the extensive hydrothermal plume emanating from the East Pacific Rise (EPR). Specifically, we have analyzed dissolved 230Th concentrations at high-resolution within the water column at two locations (ML1208-12CTD; 8° 19.989' N, 159° 18.000' W, and ML1208-03CTD; 00° 13.166' S, 155° 57.668' W) sampled as part of a cruise to the Line Islands. The pattern of the dissolved 230Th concentration profile at 8°N is essentially linear from the surface to 2000 m and generally follows a reversible scavenging model. However, from 2000 m to 3000 m, the dissolved 230Th concentrations are constant, before linearly increasing again from 3000 m to the bottom. At this site dissolved 230Th concentrations range from 1.06 fg/kg at 100 m to 55.15 fg/kg at 4600 m. At the equator, dissolved 230Th concentrations are slightly lower, and range from undetectable at 25 m to 19.07 fg/kg at 3038 m. A nearly indistinguishable pattern in dissolved 230Th concentrations occurs in the profile at the equator compared to that from 8°N. The deep-water deviation from linearity between 2 and 3 km in the 230Th profiles (lower concentrations than expected) at both sites coincides well with the interval of the water column which has the highest concentrations of 3He. This 3He-rich signal has been traced to hydrothermal plumes from the EPR, thousands of km away (Lupton et al., 1998). We hypothesize that the lower concentrations of 230Th in deep waters of the central equatorial Pacific are a result of: 1) scavenging of water-column 230Th by Fe-Mn particulates contained within the EPR hydrothermal plume, and 2) lateral export of these 230Th-deficient deep waters approximately 7000 km westward. We will discuss the implications that the transport of this signature across vast distances has on water residence and transport times. Reference: Lupton, J. (1998) J. Geophys. Res. 103, 15,853-15,868.

Engineered in situ bioremediation of a petroleum hydrocarbon-contaminated aquifer: assessment of mineralization based on alkalinity, inorganic carbon and stable carbon isotope balances

NASA Astrophysics Data System (ADS)

Hunkeler, Daniel; Höhener, Patrick; Bernasconi, Stefano; Zeyer, Josef

1999-04-01

A concept is proposed to assess in situ petroleum hydrocarbon mineralization by combining data on oxidant consumption, production of reduced species, CH 4, alkalinity and dissolved inorganic carbon (DIC) with measurements of stable isotope ratios. The concept was applied to a diesel fuel contaminated aquifer in Menziken, Switzerland, which was treated by engineered in situ bioremediation. In the contaminated aquifer, added oxidants (O 2 and NO 3-) were consumed, elevated concentrations of Fe(II), Mn(II), CH 4, alkalinity and DIC were detected and the DIC was generally depleted in 13C compared to the background. The DIC production was larger than expected based on the consumption of dissolved oxidants and the production of reduced species. Stable carbon isotope balances revealed that the DIC production in the aquifer originated mainly from microbial petroleum hydrocarbon mineralization, and that geochemical reactions such as carbonate dissolution produced little DIC. This suggests that petroleum hydrocarbon mineralization can be underestimated if it is determined based on concentrations of dissolved oxidants and reduced species.

Speciation in the Fe(III)-Cl(I)-H2O System at 298.15 K, 313.15 K, and 333.15 K (25 °C, 40 °C, and 60 °C)

NASA Astrophysics Data System (ADS)

Jamett, Nathalie E.; Hernández, Pía C.; Casas, Jesús M.; Taboada, María E.

2018-02-01

This article presents the results on speciation of ferric iron generated by the dissolution of chemical reagent hydromolysite (ferric chloride hexahydrate, FeCl3:6H2O) in water at 298.15 K, 313.15 K, and 333.15 K (25 °C, 40 °C, and 60 °C). Experiments were performed with a thermoregulated system up to the equilibrium point, as manifested by solution pH. Solution samples were analyzed in terms of concentration, pH, and electrical conductivity. Measurements of density and refractive index were obtained at different temperatures and iron concentrations. A decrease of pH was observed with the increase in the amount of dissolved iron, indicating that ferric chloride is a strong electrolyte that reacts readily with water. Experimental results were modeled using the hydrogeochemical code PHREEQC in order to obtain solution speciation. Cations and neutral and anion complexes were simultaneously present in the system at the studied conditions according to model simulations, where dominant species included Cl-, FeCl2+, FeCl2 +, FeOHCl 2 0 , and H+. A decrease in the concentration of Cl- and Fe3+ ions took place with increasing temperature due to the association of Fe-Cl species. Standard equilibrium constants for the formation of FeOHCl 2 0 obtained in this study were log Kf0 = -0.8 ± 0.01 at 298.15 K (25 °C), -0.94 ± 0.02 at 313.15 K (40 °C), and -1.03 ± 0.01 at 333.15 K (60 °C).

Solubility, Partitioning, and Speciation of Carbon in Shallow Magma Oceans of Terrestrial Planets Constrained by High P-T Experiments

NASA Astrophysics Data System (ADS)

Chi, H.; Dasgupta, R.; Shimizu, N.

2011-12-01

Deep planetary volatile cycles have a critical influence on planetary geodynamics, atmospheres, climate, and habitability. However, the initial conditions that prevailed in the early, largely molten Earth and other terrestrial planets, in terms of distribution of volatiles between various reservoirs - metals, silicates, and atmosphere - remains poorly constrained. Here we investigate the solubility, partitioning, and speciation of carbon-rich volatile species in a shallow magma ocean environment, i.e., in equilibrium with metallic and silicate melts. A series of high pressure-temperature experiments using a piston cylinder apparatus were performed at 1-3 GPa, 1500-1800 °C on synthetic basaltic mixtures + Fe-Ni metal powders contained in graphite capsules. All the experiments produced glassy silicate melt pool in equilibrium with quenched metal melt composed of dendrites of cohenite and kamacite. Major element compositions of the resulting phases and the carbon content of metallic melts were analyzed by EPMA at NASA-JSC. Carbon and hydrogen concentrations of basaltic glasses were determined using Cameca IMS 1280 SIMS at WHOI and speciation of dissolved volatiles was constrained using FTIR and Raman spectroscopy at Rice University. Based on the equilibria - FeO (silicate melt) = Fe (metal alloy melt) + 1/2O2, we estimate the oxygen fugacity of our experiments in the range of ΔIW of -1 to -2. FTIR analysis on doubly polished basaltic glass chips suggests that the concentrations of dissolved CO32- or molecular CO2 are negligible in graphite and metal saturated reduced conditions, whereas the presence of dissolved OH- is evident from the asymmetric peak at 3500 cm-1. Collected Raman spectra of basaltic glasses in the frequency range of 200-4200 cm-1 suggest that hydrogen is present both as dissolved OH- species (band at 3600 cm-1) and as molecular H2 (band near 4150 cm-1) for all of our experiments. Faint peaks near 2915 cm-1 and consistent peaks near 740 cm-1 suggest that possible carbon species in our reduced glasses are likely minor CH4 and Si-C, respectively and are consistent with the recent solubility studies at reduced conditions [1,2]. Carbon solubility (calibrated using 12C/30Si) at graphite saturation in our reduced basaltic glasses is only in the range 20-100 ppm C, with H2O contents in the range of 0.2-0.7 wt.%. In contrast to the low dissolved carbon concentration in the basaltic silicate melts, carbon solubility in quenched metallic melts vary in the range of 5-7 wt.%. Our preliminary work indicates that the solubility of carbon in reduced basaltic melts relevant for early magma conditions may be several orders of magnitude lower compared to the solubility of carbon in modern terrestrial basalts. This coupled with significant solubility of carbon in Fe-Ni metallic melt suggests that most of magma ocean carbon was likely partitioned into deep metallic melts. Further metal-silicate experiments with more depolymerized basaltic melts of variable compositions are underway and will be presented. [1] Kadik et al. JPetrol 45, 1297-1310, 2004; [2] Kadik et al. Geochem Int 44, 33-47, 2006.

Transformation of organic carbon, trace element, and organo-mineral colloids in the mixing zone of the largest European Arctic river

NASA Astrophysics Data System (ADS)

Pokrovsky, O. S.; Shirokova, L. S.; Viers, J.; Gordeev, V. V.; Shevchenko, V. P.; Chupakov, A. V.; Vorobieva, T. Y.; Candaudap, F.; Casseraund, C.; Lanzanova, A.; Zouiten, C.

2013-10-01

The estuarine behavior of organic carbon (OC) and trace elements (TE) was studied for the largest European sub-Arctic river, which is the Severnaya Dvina; this river is a deltaic estuary covered in ice during several hydrological seasons: summer (July 2010, 2012) and winter (March 2009) baseflow, and the November-December 2011 ice-free period. Colloidal forms of OC and TE were assessed using three pore size cutoff (1, 10, and 50 kDa) using an in-situ dialysis procedure. Conventionally dissolved (< 0.22 μm) fractions demonstrated clear conservative behavior for Li, B, Na, Mg, K, Ca, Sr, Mo, Rb, Cs, and U during the mixing of freshwater with the White Sea; a significant (up to a factor of 10) concentration increase occurs with increases in salinity. Si and OC also displayed conservative behavior but with a pronounced decrease of concentration seawards. Rather conservative behavior, but with much smaller changes in concentration (variation within ±30%) over a full range of salinities, was observed for Ti, Ni, Cr, As, Co, Cu, Ga, Y, and heavy REE. Strong non-conservative behavior with coagulation/removal at low salinities (< 5‰) was exhibited by Fe, Al, Zr, Hf, and light REE. Finally, certain divalent metals exhibited non-conservative behavior with a concentration gain at low (~2-5‰, Ba, Mn) or intermediate (~10-15‰, Ba, Zn, Pb, Cd) salinities, which is most likely linked to TE desorption from suspended matter or sediment outflux. The most important result of this study is the elucidation of the behavior of the "truly" dissolved low molecular weight LMW< 1 kDa fraction containing Fe, OC, and a number of insoluble elements. The concentration of the LMW fraction either remains constant or increases its relative contribution to the overall dissolved (< 0.22 μm) pool as the salinity increases. Similarly, the relative proportion of colloidal (1 kDa-0.22 μm) pool for the OC and insoluble TE bound to ferric colloids systematically decreased seaward, with the largest decrease occurring at low (< 5‰) salinities. Overall, the observed decrease of the colloidal fraction may be related to the coagulation of organo-ferric colloids at the beginning of the mixing zone and therefore the replacement of the HMW1 kDa-0.22 μm portion by the LMW< 1 kDa fraction. These patterns are highly reproducible across different sampling seasons, suggesting significant enrichment of the mixing zone by the most labile (and potentially bioavailable) fraction of the OC, Fe and insoluble TE. The size fractionation of the colloidal material during estuarine mixing reflects a number of inorganic and biological processes, the relative contribution of which to element speciation varies depending on the hydrological stage and time of year. In particular, LMW< 1 kDa ligand production in the surface horizons of the mixing zone may be linked to heterotrophic mineralization of allochthonous DOM and/or photodestruction. Given the relatively low concentration of particulate vs. dissolved load of most trace elements, desorption from the river suspended material was less pronounced than in other rivers in the world. As a result, the majority of dissolved components exhibited either a conservative (OC and related elements such as divalent metals) or non-conservative, coagulation-controlled (Fe, Al, and insoluble TE associated with organo-ferric colloids) behavior. The climate warming in high latitudes is likely to intensify the production of LMW< 1 kDa organic ligands and the associated TE; therefore, the delivery of potentially bioavailable trace metal micronutrients from the land to the ocean may increase.

Transformation of organo-ferric peat colloids by a heterotrophic bacterium

NASA Astrophysics Data System (ADS)

Oleinikova, Olga V.; Shirokova, Liudmila S.; Gérard, Emmanuele; Drozdova, Olga Yu.; Lapitskiy, Sergey A.; Bychkov, Andrey Yu.; Pokrovsky, Oleg S.

2017-05-01

Bacterial mineralization of allochthonous (soil) dissolved organic matter (DOM) in boreal waters governs the CO2 flux from the lakes and rivers to the atmosphere, which is one of the main factor of carbon balance in high latitudes. However, the fate of colloidal trace element (TE) during bacterial processing of DOM remains poorly constrained. We separated monoculture of Pseudomonas saponiphila from a boreal creek and allowed it to react with boreal Fe-rich peat leachate of approximate colloidal (3 kDa-0.45 μm) composition C1000Fe12Al3.3Mg2Ca3.7P1.2Mn0.1Ba0.5 in nutrient-free media. The total net decrease of Dissolved Organic Carbon (DOC) concentration over 4 day of exposure was within 5% of the initial value, whereas the low molecular weight fraction of Corg (LMW<3 kDa) yielded a 16%-decrease due to long-term bio-uptake or coagulation. There was a relative depletion in Fe over Corg of 0.45 μm, colloidal and LMW fraction in the course of peat leachate interaction with P. saponiphila. Al, Mn, Ni, Cu, Ga, REEs, Y, U were mostly affected by bacterial presence and exhibited essentially the adsorption at the cell surface over first hours of reaction, in contrast to Fe, Ti, Zr, and Nb that showed both short-term adsorption and long-term removal by physical coagulation/coprecipitation with Fe hydroxide. The low molecular weight fraction (LMW<3 kDa) of most TE was a factor of 2-5 less affected by microbial presence via adsorption or removal than the high molecular weight (HMW) colloidal fractions (<0.45 μm and <50 kDa). The climate change-induced acceleration of heterotrophic bacterial activity in boreal and subarctic waters may lead to preferential removal of Fe over DOC from conventionally dissolved fraction and the decrease of the proportion of LMW < 3 kDa fraction and the increase of HMW colloids. Enhanced heterotrophic mineralization of organo-ferric colloids under climate warming scenario may compensate for on-going "browning" of surface waters.

Iron [Fe(0)]-rich substrate based on iron-carbon micro-electrolysis for phosphorus adsorption in aqueous solutions.

PubMed

Deng, Shihai; Li, Desheng; Yang, Xue; Xing, Wei; Li, Jinlong; Zhang, Qi

2017-02-01

The phosphorus (P) adsorption properties of an iron [Fe(0)]-rich substrate (IRS) composed of iron scraps and activated carbon were investigated based on iron-carbon micro-electrolysis (IC-ME) and compared to the substrates commonly used in constructed wetlands (CWs) to provide an initial characterization of the [Fe(0)]-rich substrate. The results showed that P was precipitated by Fe(III) dissolved from the galvanic cell reactions in the IRS and the reaction was suppressed by the pH and stopped when the pH exceeded 8.90 ± 0.09. The adsorption capacity of the IRS decreased by only 4.6% in the second round of adsorption due to Fe(0) consumption in the first round. Substrates with high Ca- and Mg-oxide contents and high Fe- and Al-oxide contents had higher P adsorption capacities at high and low pH values, respectively. Substrates containing high Fe and Al concentrations and low Ca concentrations were more resistant to decreases in the P adsorption capacity resulting from organic matter (OM) accumulation. The IRS with an iron scrap to activated carbon volume ratio of 3:2 resulted in the highest P adsorption capacity (9.34 ± 0.14 g P kg -1 ), with minimal pH change and strong adaptability to OM accumulation. The Fe(0)-rich substrate has the considerable potential for being used as a CW substrate. Copyright © 2016 Elsevier Ltd. All rights reserved.

Role of organic acids in promoting colloidal transport of mercury from mine tailings

USGS Publications Warehouse

Slowey, A.J.; Johnson, S.B.; Rytuba, J.J.; Brown, Gordon E.

2005-01-01

A number of factors affect the transport of dissolved and paniculate mercury (Hg) from inoperative Hg mines, including the presence of organic acids in the rooting zone of vegetated mine waste. We examined the role of the two most common organic acids in soils (oxalic and citric acid) on Hg transport from such waste by pumping a mixed organic acid solution (pH 5.7) at 1 mL/min through Hg mine tailings columns. For the two total organic acid concentrations investigated (20 ??M and 1 mM), particle-associated Hg was mobilized, with the onset of paniculate Hg transport occurring later for the lower organic acid concentration. Chemical analyses of column effluent indicate that 98 wt % of Hg mobilized from the column was paniculate. Hg speciation was determined using extended X-ray absorption fine structure spectroscopy and transmission electron microscopy, showing that HgS minerals are dominant in the mobilized particles. Hg adsorbed to colloids is another likely mode of transport due to the abundance of Fe-(oxyhydr)oxides, Fe-sulfides, alunite, and jarosite in the tailings to which Hg(II) adsorbs. Organic acids produced by plants are likely to enhance the transport of colloid-associated Hg from vegetated Hg mine tailings by dissolving cements to enable colloid release. ?? 2005 American Chemical Society.

Coupled cycling of Fe and organic carbon in submarine hydrothermal systems: Modelling approach

NASA Astrophysics Data System (ADS)

Legendre, Louis; German, Christopher R.; Sander, Sylvia G.; Niquil, Nathalie

2014-05-01

It has been recently proposed that hydrothermal plumes may be a significant source of dissolved Fe to the oceans. In order to assess this proposal, we investigated the fate of dissolved Fe released from hydrothermal systems to the overlying ocean using an approach that combined modelling and field values. We based our work on a consensus conceptual model developed by members of SCOR-InterRidge Working Group 135. The model was both complex enough to capture the main processes of dissolved Fe released from hydrothermal systems and chemical transformation in the hydrothermal plume, and simple enough to be parameterized with existing field data. It included the following flows: Fe, water and heat in the high temperature vent fluids, in the fluids diffusing around the vent, and in the entrained seawater in the buoyant plume; Fe precipitation in polymetallic sulphides near the vent; transport of Fe in the non-buoyant plume, and both its precipitation in particles onto the sea bottom away from the vent and dissolution into deep-sea waters. In other words, there were three Fe input flows into the buoyant hydrothermal plume (vent-fluids; entrained diffuse flow; entrained seawater) and three Fe output flows (sedimentation from the buoyant plume as polymetallic sulfides; sedimentation from the non-buoyant plume in particulate form; export to the deep ocean in dissolved or nanoparticulate form). The output flows balanced the input flows. We transformed the conceptual model into equations, and parameterized these with field data. To do so, we assumed that all hydrothermal systems, globally, can be represented by the circumstances that prevail at the EPR 9°50'N hydrothermal field, although we knew this assumption not to be accurate. We nevertheless achieved, by following this approach, two important goals, i.e. we could assemble into a coherent framework, for the first time, several discrete data sets acquired independently over decades of field work, and we could obtain model results that were consistent with recent field observations. We used our model to explore scenarios of Fe emissions and transformations under various constraints. The modelling exercises indicated that the provision of significant amounts of dissolved Fe to the oceans by hydrothermal plumes was consistent with realistic model parameters. This supported the proposition that hydrothermal systems play significant roles in the global biogeochemical Fe cycle.

Flavins in Coastal Marine Sediments: New Perspectives on Diagenetic Electron Transfer

NASA Astrophysics Data System (ADS)

Monteverde, D.; Berelson, W.; Baronas, J. J.; Sanudo-Wilhelmy, S. A.

2016-02-01

Coastal marine sediments play a critical role in the global cycling of metals and nutrients, many of which undergo diagenetic alteration. Central to these transformations are redox reactions where electron-rich organic matter is oxidized via transfer to terminal electron acceptors (NO3-, MnOx, FeOx, SO42-). The flavins (flavin adenine dinucleotide [FAD], flavin mononucleotide [FMN], and riboflavin [B2]) are microbially synthesized organic coenzymes that perform both single and double electron transfer and are known to mediate reduction of insoluble metal oxides. Culture experiments have found high rates of flavin excretion in metal-reducing Shewanella and Geobacter species, however environmental measurements of these highly labile molecules have not been previously reported. Here we present porewater measurements of FAD, FMN, and B2 from San Pedro Basin. This California Borderland basin is silled, suboxic, 900 m deep, and experiences high sedimentation. Flavin concentrations ranged from pico- (FAD: 0- 60 pM; B2: 40 - 90 pM) to nanomolar (FMN: 0.4 - 1.2 nM). The concentration cascade of FMN>B2>FAD fits well within culture experiments. Interestingly, profiles of all three flavins show a near linear increase with depth from 0-30 cm and a relatively steady concentration from 30-45 cm, supporting likely in situ production. Additionally, the flavins showed a negative correlation with dissolved Fe (R2 = 0.7 for FMN, 0.8 for FAD, and 0.9 for B2), which decreased linearly with depth from 160µM to 65µM. We discuss hypothesized mechanisms controlling flavin concentrations based on a suite of sediment geochemical parameters (dissolved Fe, Mn, TCO2, δ13C, NH3, DOM, and SO42-) as well as implications for microbial redox syntrophy. These data provide a critical link between the extensive culture-based mechanistic understanding of flavin function and the sedimentary environment. Furthermore, these results demonstrate that flavins likely serve as a significant electron transfer intermediaries in the marine sediment carbon cycle.

Relevance of peat-draining rivers for the riverine input of dissolved iron into the ocean.

PubMed

Krachler, Regina; Krachler, Rudolf F; von der Kammer, Frank; Süphandag, Altan; Jirsa, Franz; Ayromlou, Shahram; Hofmann, Thilo; Keppler, Bernhard K

2010-05-01

Peat bogs have the ability to produce strong chelate ligands (humic and fulvic acids) which enhance the weathering rates of iron-silicate minerals and greatly increase the solubility of the essential trace metal iron in river water. Fluvial networks link peat bogs with the ocean, and thus terrestrial-derived fulvic-iron complexes fuel the ocean's biological productivity and biological carbon pump, but understanding this role is constrained by inconsistent observations regarding the behaviour of riverine iron in the estuarine mixing zone, where precipitation reactions remove iron from the water column. We applied a characterization of the colloidal iron carriers in peatland-draining rivers in North Scotland, using field-flow fractionation (FFF), in combination with end-member mixing experiments of river water sampled near the river mouth and coastal seawater using a (59)Fe radiotracer method. According to our results, the investigated river contributed "truly dissolved" Fe concentrations of about 3300nmolL(-1) to the ocean which is nearly two orders of magnitude higher than the dissolved iron contribution of the "average world" river ( approximately 40nmolL(-1)). Thus we conclude that peatland-draining rivers are important sources of dissolved iron to the ocean margins. We propose highly electrostatic and sterical stabilized iron-organic matter complexes in the size range of <2kDa to be responsible for iron transport across the estuarine mixing zone. Copyright 2010 Elsevier B.V. All rights reserved.

Intense molybdenum accumulation in sediments underneath a nitrogenous water column and implications for the reconstruction of paleo-redox conditions based on molybdenum isotopes

NASA Astrophysics Data System (ADS)

Scholz, Florian; Siebert, Christopher; Dale, Andrew W.; Frank, Martin

2017-09-01

The concentration and isotope composition of molybdenum (Mo) in sediments and sedimentary rocks are widely used proxies for anoxic conditions in the water column of paleo-marine systems. While the mechanisms leading to Mo fixation in modern restricted basins with anoxic and sulfidic (euxinic) conditions are reasonably well constrained, few studies have focused on Mo cycling in the context of open-marine anoxia. Here we present Mo data for water column particulate matter, modern surface sediments and a paleo-record covering the last 140,000 years from the Peruvian continental margin. Mo concentrations in late Holocene and Eemian (penultimate interglacial) shelf sediments off Peru range from ∼70 to 100 μg g-1, an extent of Mo enrichment that is thought to be indicative of (and limited to) euxinic systems. To investigate if this putative anomaly could be related to the occasional occurrence of sulfidic conditions in the water column overlying the Peruvian shelf, we compared trace metal (Mo, vanadium, uranium) enrichments in particulate matter from oxic, nitrate-reducing (nitrogenous) and sulfidic water masses. Coincident enrichments of iron (Fe) (oxyhydr)oxides and Mo in the nitrogenous water column as well as co-variation of dissolved Fe and Mo in the sediment pore water suggest that Mo is delivered to the sediment surface by Fe (oxyhydr)oxides. Most of these precipitate in the anoxic-nitrogenous water column due to oxidation of sediment-derived dissolved Fe with nitrate as a terminal electron acceptor. Upon reductive dissolution in the surface sediment, a fraction of the Fe and Mo is re-precipitated through interaction with pore water sulfide. The Fe- and nitrate-dependent mechanism of Mo accumulation proposed here is supported by the sedimentary Mo isotope composition, which is consistent with Mo adsorption onto Fe (oxyhydr)oxides. Trace metal co-variation patterns as well as Mo and nitrogen isotope systematics suggest that the same mechanism of Mo delivery caused the 'anomalously' high interglacial Mo accumulation rates in the paleo-record. Our findings suggest that Fe- and nitrate-dependent Mo shuttling under nitrogenous conditions needs to be considered a possible reason for sedimentary Mo enrichments during past periods of widespread anoxia in the open ocean.

The Dart estuary, Devon, UK: a case study of chemical dynamics and pollutant mobility

NASA Astrophysics Data System (ADS)

Schuwerack, P.-M. M.; Neal, M.; Neal, C.

2007-01-01

Water, sediments and gill and digestive gland tissues of adult common shore crab (Carcinus maenas), collected at Noss Marina, Sandquay (Britannia Royal Naval College), the Dartmouth Pier, Warfleet Cove and Sugary Cove in the Dart estuary, Devon, UK, were analysed for major, minor and trace elements in spring 2004. Total acid-available measurements analysed included the truly dissolved component and acid-available sediments. Trace metal concentrations are associated largely with particulate and micro-particulate/colloidal phases, the latter being able to pass through standard filter papers. Wide ranges of chemical concentrations were found in the water, sediments and tissues at all the locations. In the water column, 48% of the variance is linked to the sea-salt component (Cl, Na, K, Ca, Mg, B, Li and Sr) and the sediment-associated acid-available fractions are linked to Fe-rich lithogenous materials (Ba, Co, Cu, Fe, Mn, V and Zn). In the sediments, trace elements of Cd, Co, Cr, Fe, Pb, Mn, Ni and V are correlated with the sea salts and associated with the fraction of fine sediments within the total sediment. In the gills and the digestive gland tissues of crabs, high concentrations of Al, Cu and Fe are found and there are correlations between acid-available trace metals of Cu, Cr, Fe, Mn, Ni, Sr and Zn. The relationships between trace metal contaminants, their site-specific concentrations, their temporal and spatial variability and the effects of human activities, such as moorland/agriculture with historic mining and recreational activities in the lower Dart estuary, are discussed.

Real-time redox speciation of iron in estuarine and coastal surface waters.

PubMed

Huang, Yongming; Yuan, Dongxing; Zhu, Yong; Feng, Sichao

2015-03-17

An automated, shipboard-use system was developed for real-time speciation of iron in coastal surface waters. It comprised a towed Fish underway sampler and a modified reverse flow injection analysis system with a liquid waveguide capillary flow cell-spectrophotometric detection device. The detection was based on the reaction between ferrozine and Fe(II). The detection limits of 0.3 and 0.7 nM were achieved for Fe(II) and Fe(II+III), together with their respective dynamic linear ranges of 0.5-250 and 0.9-250 nM. The system was successfully deployed and run consecutively for about 1 week during a cruise in August 2009 to the East China Sea off the Changjiang Estuary. The distribution of operationally defined field dissolvable Fe(II) and Fe(II+III) (expressed as Fea(II) and Fea(II+III)) in these areas was obtained, which showed that both Fea(II) and Fea(II+III) concentrations decreased with salinity when there were relatively high Fea(II) concentrations (up to about 120 nM) near shore. A distinct distribution of Fea(II) to Fea(II+III) ratios was also revealed, with a ratio of 0.58 in the water off Changjiang Estuary and 0.19 in the open ocean.

Iron dissolution kinetics of mineral dust at low pH during simulated atmospheric processing

NASA Astrophysics Data System (ADS)

Shi, Z.; Bonneville, S.; Krom, M. D.; Carslaw, K. S.; Jickells, T. D.; Baker, A. R.; Benning, L. G.

2010-11-01

We investigated the iron (Fe) dissolution kinetics of African (Tibesti) and Asian (Beijing) dust samples at acidic pH with the aim of reproducing the low pH conditions in atmospheric aerosols. The Beijing dust and three size fractions of the Tibesti dust (<20 μm: PM20; <10 μm: PM10; and <2.5 μm: PM2.5) were dissolved at pH 1, 2 and/or 3 for up to 1000 h. In the first 10 min, all dust samples underwent an extremely fast Fe solubilisation. Subsequently, the Fe dissolution proceeded at a much slower rate before reaching a stable dissolution plateau. The time-dependant Fe dissolution datasets were best described by a model comprising three acid-extractable Fe pools each dissolving according to first-order kinetics. The dissolution rate constant k of each pool was independent of the source (Saharan or Asian) and the size (PM20, PM10 or PM2.5) of the dust but highly dependent on pH. The "fast" Fe pool had a k (25 h-1 at pH=1) of a similar magnitude to "dry" ferrihydrite nanoparticles and/or poorly crystalline Fe(III) oxyhydroxide, while the "intermediate" and "slow" Fe pools had k values respectively 50-60 times and 3000-4000 times smaller than the "fast" pool. The "slow" Fe pool was likely to consist of both crystalline Fe oxide phases (i.e., goethite and/or hematite) and Fe contained in the clay minerals. The initial mass of the "fast", "intermediate" and "slow" Fe pools represented respectively about 0.5-2%, 1-3% and 15-40% of the total Fe in the dust samples. Furthermore, we showed that in systems with low dust/liquid ratios, Fe can be dissolved from all three phases, whereas at high dust/liquid ratios (e.g., in aerosols), sufficient Fe is solubilised from the "fast" phase to dominate the Fe dissolved and to suppress the dissolution of Fe from the other Fe pools. These data demonstrated that dust/liquid ratio and pH are fundamental parameters controlling Fe dissolution kinetics in the dust. In order to reduce errors in atmospheric and climate models, these fundamental controlling factors need to be included.

Iron dissolution kinetics of mineral dust at low pH during simulated atmospheric processing

NASA Astrophysics Data System (ADS)

Shi, Z.; Bonneville, S.; Krom, M. D.; Carslaw, K. S.; Jickells, T. D.; Baker, A. R.; Benning, L. G.

2011-02-01

We investigated the iron (Fe) dissolution kinetics of African (Tibesti) and Asian (Beijing) dust samples at acidic pH with the aim of reproducing the low pH conditions in atmospheric aerosols. The Beijing dust and three size fractions of the Tibesti dust (<20 μm: PM20; <10 μm: PM10; and <2.5 μm: PM2.5) were dissolved at pH 1, 2 and/or 3 for up to 1000 h. In the first 10 min, all dust samples underwent an extremely fast Fe solubilisation. Subsequently, the Fe dissolution proceeded at a much slower rate before reaching a stable dissolution plateau. The time-dependant Fe dissolution datasets were best described by a model comprising three acid-extractable Fe pools each dissolving according to first-order kinetics. The dissolution rate constant k (h-1) of each pool was independent of the source (Saharan or Asian) and the size (PM20, PM10 or PM2.5) of the dust but highly dependent on pH. The "fast" Fe pool had a k (25 h-1 at pH = 1) of a similar magnitude to "dry" ferrihydrite nanoparticles and/or poorly crystalline Fe(III) oxyhydroxide, while the "intermediate" and "slow" Fe pools had k values respectively 50-60 times and 3000-4000 times smaller than the "fast" pool. The "slow" Fe pool was likely to consist of both crystalline Fe oxide phases (i.e., goethite and/or hematite) and Fe contained in the clay minerals. The initial mass of the "fast", "intermediate" and "slow" Fe pools represented respectively about 0.5-2%, 1-3% and 15-40% of the total Fe in the dust samples. Furthermore, we showed that in systems with low dust/liquid ratios, Fe can be dissolved from all three pools, whereas at high dust/liquid ratios (e.g., in aerosols), sufficient Fe may be solubilised from the "fast" phase to dominate the Fe dissolved and to suppress the dissolution of Fe from the other Fe pools. These data demonstrated that dust/liquid ratio and pH are fundamental parameters controlling Fe dissolution kinetics in the dust. In order to reduce errors in atmospheric and climate models, these fundamental controlling factors need to be included.

Abundance, size distributions and trace-element binding of organic and iron-rich nanocolloids in Alaskan rivers, as revealed by field-flow fractionation and ICP-MS

NASA Astrophysics Data System (ADS)

Stolpe, Björn; Guo, Laodong; Shiller, Alan M.; Aiken, George R.

2013-03-01

Water samples were collected from six small rivers in the Yukon River basin in central Alaska to examine the role of colloids and organic matter in the transport of trace elements in Northern high latitude watersheds influenced by permafrost. Concentrations of dissolved organic carbon (DOC), selected elements (Al, Si, Ca, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Rb, Sr, Ba, Pb, U), and UV-absorbance spectra were measured in 0.45 μm filtered samples. 'Nanocolloidal size distributions' (0.5-40 nm, hydrodynamic diameter) of humic-type and chromophoric dissolved organic matter (CDOM), Cr, Mn, Fe, Co, Ni, Cu, Zn, and Pb were determined by on-line coupling of flow field-flow fractionation (FFF) to detectors including UV-absorbance, fluorescence, and ICP-MS. Total dissolved and nanocolloidal concentrations of the elements varied considerably between the rivers and between spring flood and late summer base flow. Data on specific UV-absorbance (SUVA), spectral slopes, and the nanocolloidal fraction of the UV-absorbance indicated a decrease in aromaticity and size of CDOM from spring flood to late summer. The nanocolloidal size distributions indicated the presence of different 'components' of nanocolloids. 'Fulvic-rich nanocolloids' had a hydrodynamic diameter of 0.5-3 nm throughout the sampling season; 'organic/iron-rich nanocolloids' occurred in the <8 nm size range during the spring flood; whereas 'iron-rich nanocolloids' formed a discrete 4-40 nm components during summer base flow. Mn, Co, Ni, Cu and Zn were distributed between the nanocolloid components depending on the stability constant of the metal (+II)-organic complexes, while stronger association of Cr to the iron-rich nanocolloids was attributed to the higher oxidation states of Cr (+III or +IV). Changes in total dissolved element concentrations, size and composition of CDOM, and occurrence and size of organic/iron and iron-rich nanocolloids were related to variations in their sources from either the upper organic-rich soil or the deeper mineral layer, depending on seasonal variations in hydrological flow patterns and permafrost dynamics.

Anoxic groundwaters as a source of CO2 and PO4 for the coastal southern Baltic Sea: The role of an iron curtain

NASA Astrophysics Data System (ADS)

Lipka, Marko; Schneider, Jonas; Schmiedinger, Iris; Westphal, Julia; Escher, Peter; Sültenfuß, Jürgen; Dellwig, Olaf; Winde, Vera; Böttcher, Michael E.

2017-04-01

Submarine ground water discharge (SGD) into coastal ecosystems is perceived as an important source of fresh water and solutes (nutrients, metabolites, trace elements) in marine biogeochemical cycles. Less is known about its significance for the German coastal zone. We present here the results of hydrogeochemical and stable isotope geochemical studies in an area that is affected by SGD into the southern Baltic Sea. Anoxic groundwaters emerging as springs at the shore zone of the southern Baltic Sea are windows into the composition of subterrestrial ground water composition. They were investigated on a seasonal base for about five years. Water samples were analyzed for the concentrations of major and trace elements, pH, and the stable isotope ratios of water, DIC and sulfate. Newly formed precipitates in the stream bed were characterized via SEM-EDX and the stable isotope composition, as well as chemically extracted for the determination of the solid composition. The springs emerge in small pits yielding discharges of about 10 l/min each. Surrounding sediments are sandy with gravels found at depth and corresponding high permeabilities. The positions of different springs on the shore zone were geostationary during the investigation period while their shape varied due to wind- and wave action. The 2H and 18O contents of the spring waters indicate the ground water to originate from relatively young mixed meteoric waters. Dating by means of tritium and noble gases (3H, 3He, 4He, Ne) yields an age of the spring waters of about 25-32 years, with different mixing proportions of tritium-free waters. The springs are hydrogeochemically characterized by dissolved Ca, Mg, Na, bicarbonate, and sulfate, mainly reflecting the water-rock interaction with aquifer material in the recharge area. The isotope signature of DIC indicates the uptake of biogenic CO2 in the soil zone followed by the dissolution of carbonate minerals in the soil/ aquifer system. The oxygen-free ground water is rich in dissolved iron (Fe) and phosphorous (P). Iron(oxyhydr)oxide precipitates in the stream beds acting as a sink for dissolved PO4 and minor Ca. The investigation reveals that the surface precipitation on the beach leads to the formation of submarine groundwater discharge essentially free of dissolved Fe and PO4. The formation of Fe-phases in the subterranean estuary is supposed at depth influencing the release of nutrients and metals into the coastal ecosystem. Before the water passes to underground drainage into a subterranean mixing zone with brackish Baltic Sea waters, the above ground draining streams degas carbon dioxide and take up oxygen in contact with the atmosphere. Iron(oxyhydr)oxide precipitates in the stream beds acting as a sink for dissolved phosphate. Residues of Fe- oxidizing bacteria were found in the stream bed rust indicating an involvement of microbes to catalyze the dissolved Fe removal. The investigation reveals that the surface precipitation on the beach leads to the formation of submarine groundwater discharge essentially free of dissolved iron and phosphate. The formation of Fe-phases in the subterranean estuary is also supposed to take place at depth thereby influencing the release of nutrients and metals into the Baltic Sea coastal ecosystem. This work was supported by the BONUS+ project AMBER, the Leibniz IOW and the Graduiertenkolleg BALTIC TRANSCOAST.

Microbial Transport Mechanisms in Silty, Sandy Media as Inferred From Short Core Experiments Performed in the Field.

NASA Astrophysics Data System (ADS)

Mailloux, B.; Hall, j; Fuller, M.; Scheibe, T.; DeFlaun, M.; Onstott, T.

2001-12-01

A novel approach to examining the mechanisms controlling the velocity and attachment of bacteria in porous media was developed for the South Oyster Bacterial Transport Field Site. Instead of performing bacterial transport experiments in the lab using repacked materials and artificial water, samples of sediment core, 7 cm. in length, were connected to multi-level samplers at the field site, the groundwater from select levels in the aquifer was pumped through the cores, and an aliquot of cells stained with a viable, fluorescent dye was injected with Br into the influent end of the cores. The same cells, Br and groundwater were simultaneously passed through repacked cores composed of sieved sand of varying grain size fractions (100 to 600  diameter) and a single grain size fraction coated with Fe and Al synthetic oxides. The grain size of the coated sand and the Fe and Al concentrations of the coated sand (500 to 1000 ppm) were representative of the average value of the aquifer. By using this approach, the parameters that are difficult to reproduce in the lab, e.g., the dissolved gas concentrations, pH, temperature, dissolved organic matter, the indigenous bacterial and protist populations, could be replicated. One of the results derived from 29 short core experiments indicate that the enhanced velocity of adhesion deficient DA001 that has been reported in laboratory experiments was greatly reduced in the field experiments for the Fe and Al coated sands and greatly enhanced for the fine grained sands.

Changes of the corrosion potential of iron in stagnation and flow conditions and their relationship with metal release.

PubMed

Fabbricino, Massimiliano; Korshin, Gregory V

2014-10-01

This study examined the behavior of corrosion potential (Ecorr) of iron exposed to drinking water during episodes of stagnation and flow. These measurements showed that during stagnation episodes, Ecorr values decrease prominently and consistently. This decrease is initially rapid but it becomes slower as the stagnation time increases. During flow episodes, the Ecorr values increase and reach a quasi-steady state. Experiments with varying concentrations of dissolved oxygen showed that the decrease of Ecorr values characteristic for stagnation is likely to be associated with the consumption of dissolved oxygen by the exposed metal. The corrosion potential of iron and its changes during stagnation were sensitive to the concentrations of sulfate and chloride ions. Measurements of iron release showed that both the absolute values of Ecorr measured prior to or after stagnation episodes were well correlated with the logarithms of concentrations of total iron. The slope of this dependence showed that the observed correlations between Ecorr values and Fe concentrations corresponded to the coupling between the oxidant consumption and changes of Fe redox status. These results demonstrate that in situ Ecorr measurements can be a sensitive method with which to ascertain effects of hydrodynamic conditions and short-term variations of water chemistry on metal release and corrosion in drinking water. This approach is valuable practically because Ecorr measurements are precise, can be carried out in situ with any desired time resolution, do not affect the state of exposed surface in any extent and can be carried out with readily available equipment. Copyright © 2014 Elsevier Ltd. All rights reserved.

Concentrations and distributions of metals associated with dissolved organic matter from the Suwannee River (GA, USA)

USGS Publications Warehouse

Kuhn, M. Keshia; Neubauer, Elisabeth; Hofmann, Thilo; von der Kammer, Frank; Aiken, George R.; Maurice, Patricia A.

2015-01-01

Concentrations and distributions of metals in Suwannee River (SR) raw filtered surface water (RFSW) and dissolved organic matter (DOM) processed by reverse osmosis (RO), XAD-8 resin (for humic and fulvic acids [FA]), and XAD-4 resin (for “transphilic” acids) were analyzed by asymmetrical flow field-flow fractionation (AsFlFFF). SR samples were compared with DOM samples from Nelson's Creek (NLC), a wetland-draining stream in northern Michigan; previous International Humic Substances Society (IHSS) FA and RO samples from the SR; and an XAD-8 sample from Lake Fryxell (LF), Antarctica. Despite application of cation exchange during sample processing, all XAD and RO samples contained substantial metal concentrations. AsFlFFF fractograms allowed metal distributions to be characterized as a function of DOM component molecular weight (MW). In SR RFSW, Fe, Al, and Cu were primarily associated with intermediate to higher than average MW DOM components. SR RO, XAD-8, and XAD-4 samples from May 2012 showed similar MW trends for Fe and Al but Cu tended to associate more with lower MW DOM. LF DOM had abundant Cu and Zn, perhaps due to amine groups that should be present due to its primarily algal origins. None of the fractograms showed obvious evidence for mineral nanoparticles, although some very small mineral nanoparticles might have been present at trace concentrations. This research suggests that AsFlFFF is important for understanding how metals are distributed in different DOM samples (including IHSS samples), which may be key to metal reactivity and bioavailability.

Arctic Deep Water Ferromanganese-Oxide Deposits Reflect the Unique Characteristics of the Arctic Ocean

NASA Astrophysics Data System (ADS)

Hein, James R.; Konstantinova, Natalia; Mikesell, Mariah; Mizell, Kira; Fitzsimmons, Jessica N.; Lam, Phoebe J.; Jensen, Laramie T.; Xiang, Yang; Gartman, Amy; Cherkashov, Georgy; Hutchinson, Deborah R.; Till, Claire P.

2017-11-01

Little is known about marine mineral deposits in the Arctic Ocean, an ocean dominated by continental shelf and basins semi-closed to deep-water circulation. Here, we present data for ferromanganese crusts and nodules collected from the Amerasia Arctic Ocean in 2008, 2009, and 2012 (HLY0805, HLY0905, and HLY1202). We determined mineral and chemical compositions of the crusts and nodules and the onset of their formation. Water column samples from the GEOTRACES program were analyzed for dissolved and particulate scandium concentrations, an element uniquely enriched in these deposits. The Arctic crusts and nodules are characterized by unique mineral and chemical compositions with atypically high growth rates, detrital contents, Fe/Mn ratios, and low Si/Al ratios, compared to deposits found elsewhere. High detritus reflects erosion of submarine outcrops and North America and Siberia cratons, transport by rivers and glaciers to the sea, and distribution by sea ice, brines, and currents. Uniquely high Fe/Mn ratios are attributed to expansive continental shelves, where diagenetic cycling releases Fe to bottom waters, and density flows transport shelf bottom water to the open Arctic Ocean. Low Mn contents reflect the lack of a mid-water oxygen minimum zone that would act as a reservoir for dissolved Mn. The potential host phases and sources for elements with uniquely high contents are discussed with an emphasis on scandium. Scandium sorption onto Fe oxyhydroxides and Sc-rich detritus account for atypically high scandium contents. The opening of Fram Strait in the Miocene and ventilation of the deep basins initiated Fe-Mn crust growth ˜15 Myr ago.

Arctic deep-water ferromanganese-oxide deposits reflect the unique characteristics of the Arctic Ocean

USGS Publications Warehouse

Hein, James; Konstantinova, Natalia; Mikesell, Mariah; Mizell, Kira; Fitzsimmons, Jessica N.; Lam, Phoebe; Jensen, Laramie T.; Xiang, Yang; Gartman, Amy; Cherkashov, Georgy; Hutchinson, Deborah; Till, Claire P.

2017-01-01

Little is known about marine mineral deposits in the Arctic Ocean, an ocean dominated by continental shelf and basins semi-closed to deep-water circulation. Here, we present data for ferromanganese crusts and nodules collected from the Amerasia Arctic Ocean in 2008, 2009, and 2012 (HLY0805, HLY0905, HLY1202). We determined mineral and chemical compositions of the crusts and nodules and the onset of their formation. Water column samples from the GEOTRACES program were analyzed for dissolved and particulate scandium concentrations, an element uniquely enriched in these deposits.The Arctic crusts and nodules are characterized by unique mineral and chemical compositions with atypically high growth rates, detrital contents, Fe/Mn ratios, and low Si/Al ratios, compared to deposits found elsewhere. High detritus reflects erosion of submarine outcrops and North America and Siberia cratons, transport by rivers and glaciers to the sea, and distribution by sea ice, brines, and currents. Uniquely high Fe/Mn ratios are attributed to expansive continental shelves, where diagenetic cycling releases Fe to bottom waters, and density flows transport shelf bottom water to the open Arctic Ocean. Low Mn contents reflect the lack of a mid-water oxygen minimum zone that would act as a reservoir for dissolved Mn. The potential host phases and sources for elements with uniquely high contents are discussed with an emphasis on scandium. Scandium sorption onto Fe oxyhydroxides and Sc-rich detritus account for atypically high scandium contents. The opening of Fram Strait in the Miocene and ventilation of the deep basins initiated Fe-Mn crust growth ∼15 Myr ago.

Release of 226Ra from uranium mill tailings by microbial Fe(III) reduction

USGS Publications Warehouse

Landa, E.R.; Phillips, E.J.P.; Lovley, D.R.

1991-01-01

Uranium mill tailings were anaerobically incubated in the presence of H2 with Alteromonas putrefaciens, a bacterium known to couple the oxidation of H2 and organic compounds to the reduction of Fe(III) oxides. There was a direct correlation between the extent of Fe(III) reduction and the accumulation of dissolved 226Ra. In sterile tailings in which Fe(III) was not reduced, there was negligible leaching of 226Ra. The behavior of Ba was similar to that of Ra in inoculated and sterile systems. These results demonstrate that under anaerobic conditions, microbial reduction of Fe(III) may result in the release of dissolved 226Ra from uranium mill tailings. ?? 1991.

Geochemical drivers of organic matter decomposition in Arctic tundra soils

DOE PAGES

Herndon, Elizabeth M.; Yang, Ziming; Graham, David E.; ...

2015-12-07

Climate change is warming tundra ecosystems in the Arctic, resulting in the decomposition of previously-frozen soil organic matter (SOM) and release of carbon (C) to the atmosphere; however, the processes that control SOM decomposition and C emissions remain highly uncertain. In this study, we evaluate geochemical factors that influence anaerobic production of carbon dioxide (CO 2) and methane (CH 4) in the active layers of four ice-wedge polygons. Surface and soil pore waters were collected during the annual thaw season over a two-year period in an area containing waterlogged, low-centered polygons and well-drained, high-centered polygons. We report spatial and seasonalmore » patterns of dissolved gases in relation to the geochemical properties of Fe and organic C as determined using spectroscopic and chromatographic techniques. Iron was present as Fe(II) in soil solution near the permafrost boundary but enriched as Fe(III) in the middle of the active layer, similar to dissolved aromatic-C and organic acids. Dissolved CH 4 increased relative to dissolved CO 2 with depth and varied with soil moisture in the middle of the active layer in patterns that were positively correlated with the proportion of dissolved Fe(III) in transitional and low-centered polygon soils but negatively correlated in the drier flat- and high-centered polygons. These results suggest that microbial-mediated Fe oxidation and reduction influence respiration/fermentation of SOM and production of substrates (e.g., low-molecular-weight organic acids) for methanogenesis. As a result, we infer that geochemical differences induced by water saturation dictate microbial products of SOM decomposition, and Fe geochemistry is an important factor regulating methanogenesis in anoxic tundra soils.« less

Transient changes in shallow groundwater chemistry during the MSU ZERT CO2 injection experiment

USGS Publications Warehouse

Apps, J.A.; Zheng, Lingyun; Spycher, N.; Birkholzer, J.T.; Kharaka, Y.; Thordsen, J.; Kakouros, E.; Trautz, R.

2011-01-01

Food-grade CO2 was injected into a shallow aquifer through a perforated pipe placed horizontally 1-2 m below the water table at the Montana State University Zero Emission Research and Technology (MSU-ZERT) field site at Bozeman, Montana. The possible impact of elevated CO2 levels on groundwater quality was investigated by analyzing 80 water samples taken before, during, and following CO2 injection. Field determinations and laboratory analyses showed rapid and systematic changes in pH, alkalinity, and conductance, as well as increases in the aqueous concentrations of trace element species. The geochemical data were first evaluated using principal component analysis (PCA) in order to identify correlations between aqueous species. The PCA findings were then used in formulating a geochemical model to simulate the processes likely to be responsible for the observed increases in the concentrations of dissolved constituents. Modeling was conducted taking into account aqueous and surface complexation, cation exchange, and mineral precipitation and dissolution. Reasonable matches between measured data and model results suggest that: (1) CO2 dissolution in the groundwater causes calcite to dissolve. (2) Observed increases in the concentration of dissolved trace metals result likely from Ca+2-driven ion exchange with clays (smectites) and sorption/desorption reactions likely involving Fe (hydr)oxides. (3) Bicarbonate from CO2 dissolution appears to compete for sorption with anionic species such as HAsO4-2, potentially increasing dissolved As levels in groundwater. ?? 2011 Published by Elsevier Ltd.

Is browning a trigger for dominance of harmful cyanobacteria species in lakes?

NASA Astrophysics Data System (ADS)

Freeman, E. C.; Creed, I. F.

2017-12-01

"Browning" is the increase of dissolved organic matter (DOM) loads into aquatic ecosystems. It is typified by an increase in the color of surface waters as well as an increase in iron (Fe) concentrations. Browning, has been observed in boreal and temperate lakes of the northern hemisphere. This phenomena has implications for freshwater ecosystems by shifting microbial community compositions, influencing the nutritional quality of autotrophs in terms of their stoichiometry, fatty acid composition, toxin production, and methylmercury concentration, and therefore, contaminant transfer through the anabolic food web. We hypothesize that browning of lake waters will increase the dominance of particular species of cyanobacteria with adaptations to lower light, mixotrophic tendencies, and specialized Fe-uptake mechanisms. Here, we present results from a high resolution real-time monitoring campaign of an Ontario lake during the growing season where the toxin-producing cyanobacteria Plantothrix Isothrix is the dominant species. We observe the changes in phytoplankton composition, Fe concentrations, and DOM. These observations are paired with a series of controlled in-lake bottle bioassay experiments that test the role of Fe in controlling the growth of Planktothix Isothrix. In a three-way factorial design, with additions of the macronutrients phosphorus and nitrogen, we explore the effects of Fe removal and addition on the phytoplankton community composition. Understanding the interaction between the effects of browning and toxin-producing phytoplankton gives insight into the dominance of cyanobacteria in a browner world, and the potential risks to aquatic ecosystems and the services they provide.

Bioenhanced dissolution of dense non-aqueous phase of trichloroethylene as affected by iron reducing conditions: model systems and environmental samples.

PubMed

Paul, Laiby; Smolders, Erik

2015-01-01

The anaerobic biotransformation of trichloroethylene (TCE) can be affected by competing electron acceptors such as Fe (III). This study assessed the role of Fe (III) reduction on the bioenhanced dissolution of TCE dense non-aqueous phase liquid (DNAPL). Columns were set up as 1-D diffusion cells consisting of a lower DNAPL layer, a layer with an aquifer substratum and an upper water layer that is regularly refreshed. The substrata used were either inert sand or sand coated with 2-line ferrihydrite (HFO) or two environmental Fe (III) containing samples. The columns were inoculated with KB-1 and were repeatedly fed with formate. In none of the diffusion cells, vinyl chloride or ethene was detected while dissolved and extractable Fe (II) increased strongly during 60 d of incubation. The cis-DCE concentration peaked at 4.0 cm from the DNAPL (inert sand) while it was at 3.4 cm (sand+HFO), 1.7 cm and 2.5 cm (environmental samples). The TCE concentration gradients near the DNAPL indicate that the DNAPL dissolution rate was larger than that in an abiotic cell by factors 1.3 (inert sand), 1.0 (sand+HFO) and 2.2 (both environmental samples). This results show that high bioavailable Fe (III) in HFO reduces the TCE degradation by competitive Fe (III) reduction, yielding lower bioenhanced dissolution. However, Fe (III) reduction in environmental samples was not reducing TCE degradation and the dissolution factor was even larger than that of inert sand. It is speculated that physical factors, e.g. micro-niches in the environmental samples protect microorganisms from toxic concentrations of TCE. Copyright © 2014 Elsevier Ltd. All rights reserved.

The role of iron and reactive oxygen species in the production of CO2 in arctic soil waters

NASA Astrophysics Data System (ADS)

Trusiak, Adrianna; Treibergs, Lija A.; Kling, George W.; Cory, Rose M.

2018-03-01

Hydroxyl radical (radOH) is a highly reactive oxidant of dissolved organic carbon (DOC) in the environment. radOH production in the dark was observed through iron and DOC mediated Fenton reactions in natural environments. Specifically, when dissolved oxygen (O2) was added to low oxygen and anoxic soil waters in arctic Alaska, radOH was produced in proportion to the concentrations of reduced iron (Fe(II)) and DOC. Here we demonstrate that Fe(II) was the main electron donor to O2 to produce radOH. In addition to quantifying radOH production, hydrogen peroxide (H2O2) was detected in soil waters as a likely intermediate in radOH production from oxidation of Fe(II). For the first time in natural systems we detected carbon dioxide (CO2) production from radOH oxidation of DOC. More than half of the arctic soil waters tested showed production of CO2 under conditions conducive for production of radOH. Findings from this study strongly suggest that DOC is the main sink for radOH, and that radOH can oxidize DOC to yield CO2. Thus, this iron-mediated, dark chemical oxidation of DOC may be an important component of the arctic carbon cycle.

Effects of solution chemistry on arsenic(V) removal by low-cost adsorbents.

PubMed

Wang, Yuru; Tsang, Daniel C W

2013-11-01

Natural and anthropogenic arsenic (As) contamination of water sources pose serious health concerns, especially for small communities in rural areas. This study assessed the applicability of three industrial byproducts (coal fly ash, lignite, and green waste compost) as the low-cost adsorbents for As(V) removal under various field-relevant conditions (dissolved oxygen, As(V)/Fe ratio, solution pH, and presence of competing species). The physico-chemical properties of the adsorbents were characterized by XRD, XRF, FT-IR, and NMR analysis. Batch experiments demonstrated that coal fly ash could provide effective As(V) removal (82.1%-95%) because it contained high content of amorphous iron/aluminium hydroxides for As(V) adsorption and dissolvable calcium minerals for calcium arsenate precipitation. However, the addition of lignite and green waste compost was found unfavourable since they hindered the As(V) removal by 10%-42% possibly due to dissolution of organic matter and ternary arsenate-iron-organic matter complexes. On the other hand, higher concentrations of dissolved iron (comparing As(V)/Fe ratios of 1:1 and 1:10) and dissolved oxygen (comparing 0.2 and 6 mg/L) only marginally enhanced the As(V) removal at pH 6 and 8. Thus, addition of dissolved iron, water aeration, or pH adjustment became unnecessary because coal fly ash was able to provide effective As(V) removal under the natural range of geochemical conditions. Moreover, the presence of low levels of background competing (0.8 or 8 mg/L of humic acid, phosphate, and silicate) imposed little influence on As(V) removal, possibly because the high adsorption capacity of coal fly ash was far from exhaustion. These results suggested that coal fly ash was a potentially promising adsorbent that warranted further investigation.

Transfer Behavior of the Weakly Acidic BCS Class II Drug Valsartan from the Stomach to the Small Intestine During Fasted and Fed States.

PubMed

Hamed, Rania; Alnadi, Sabreen Hasan

2018-05-07

The objective of this study was to investigate the transfer behavior of the weakly acidic BCS class II drug valsartan from the stomach to the small intestine during fasted and fed states. An in vitro transfer model previously introduced by Kostewicz et al. (J Pharm Pharmacol 56(1):43-51, 2004) based on a syringe pump and a USP paddle apparatus was used to determine the concentration profiles of valsartan in the small intestine. Donor phases of simulated gastric fluid during fasted (FaSSGF) and fed (FeSSGF) states were used to predisperse Diovan® tablets (160 mg valsartan). The initial concentrations of valsartan in FaSSGF and FeSSGF were 6.2 and 91.8%, respectively. Valsartan dispersions were then transferred to acceptor phases that simulate intestinal fluid and cover the physiological properties (pH, buffer capacity, and ionic strength) of the gastrointestinal fluid at a flow rate of 2 mL/min. The pH measurements were reported at time intervals corresponded to those of the transfer experiments to investigate the effect of percent dissolved of valsartan in the donor phase on lowering the pH of the acceptor phases. The f2 similarity test was used to compare the concentration profiles in the acceptor phases. In fasted state, the concentration of valsartan in the acceptor phases ranged between 33.1 and 89.4% after 240 min. Whereas in fed state, valsartan was fully dissolved in all acceptor phases within a range of 94.5-104.9% after 240 min. Therefore, the transfer model provides a useful screen for the concentrations of valsartan in the small intestine during fasted and fed states.

Observed And Modeled Seasonal Trends In Dissolved And Particulate Cu, Fe, Mn, And Zn In A Mining-Impacted Stream

EPA Science Inventory

North Fork Clear Creek (NFCC) in Colorado, an acid-mine drainage (AMD) impacted stream, was chosen to examine the distribution of dissolved and particulate Cu, Fe, Mn, and Zn in the water column, with respect to seasonal hydrologic controls. NFCC is a high-gradient stream with d...

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zhang, Fan; Parker, Jack C.; Brooks, Scott C

This study investigated sorption of uranium and technetium onto aluminum and iron hydroxides during titration of a contaminated groundwater using both Na hydroxide and carbonate as titrants. The contaminated groundwater has a low pH of 3.8 and high concentrations of NO3-, SO42-, Al, Ca, Mg, Mn, trace metals such as Ni and Co, and radionuclides such as U and Tc. During titration, most Al and Fe were precipitated out at pH above ~4.5. U as well as Tc was found to be removed from aqueous phase at pH below ~5.5, but to some extent released at higher pH values. Anmore » earlier geochemical equilibrium reaction path model that considered aqueous complexation and precipitation/dissolution reactions predicted mineral precipitation and adequately described concentration variations of Al, Fe and some other metal cations, but failed to predict sulfate, U and Tc concentrations during titration. Previous studies have shown that Fe- and Al-oxyhydroxides strongly sorb dissolved sulfate, U and Tc species. Therefore, an anion exchange model was developed for the sorption of sulfate, U and Tc onto Al and Fe hydroxides. With the additional consideration of the anion exchange reactions, concentration profiles of sulfate, U and Tc were more accurately predicted. Results of this study indicate that consideration of complex reactions such as sorption/desorption on mixed mineral phases, in addition to hydrolysis and precipitation, could improve the prediction of various contaminants during pre- and post-groundwater treatment practices.« less

Tracing water and suspended matter in Raritan and Lower New York Bays using dissolved and particulate elemental concentrations

USGS Publications Warehouse

Paulson, A.J.

2005-01-01

The concentrations of 22 elements also were measured in the suspended matter of Raritan and Lower New York Bays and brackish water sources. The elemental composition of the suspended matter in surface and bottom waters was correlated with Fe concentrations, which ranged between 50 and 900 μmol g− 1. Statistical differences among the geographical regions were detected in the relationships of Ti, Ni, Co, As, and U with Fe, with particulate As being an especially strong geochemical indicator of Raritan River particles. The geochemical signatures of Lower New York Bay particles were similar to those of Upper New York Bay. The geochemical signatures of Raritan River particles were distinctly different than those of the Upper New York Bay, but the influence of Raritan River particles appeared to be limited to only inner Raritan Bay. This study illustrates the utility of trace elements for characterization of physical processes in complex estuaries.

Mobilization of Trace Metals in an Experimental Carbon Sequestration Scenario

NASA Astrophysics Data System (ADS)

Marcon, V.; Kaszuba, J. P.

2012-12-01

Mobilizing trace metals with injection of supercritical CO2 into deep saline aquifers is a concern for geologic carbon sequestration. The potential for leakage from these systems requires an understanding of how injection reservoirs interact with the overlying potable aquifers. Hydrothermal experiments were performed to evaluate metal mobilization and mechanisms of release in a carbonate storage reservoir and at the caprock-reservoir boundary. Experiments react synthetic Desert Creek limestone and/or Gothic Shale, formations in the Paradox Basin, Utah, with brine that is close to equilibrium with these rocks. A reaction temperature of 1600C accelerates the reaction kinetics without changing in-situ water-rock reactions. The experiments were allowed to reach steady state before injecting CO2. Changes in major and trace element water chemistry, dissolved carbon and sulfide, and pH were tracked throughout the experiments. CO2 injection decreases the pH by 1 to 2 units; concomitant mineral dissolution produces elevated Ba, Cu, Fe, Pb, and Zn concentrations in the brine. Concentrations subsequently decrease to approximately steady state values after 120-330 hours, likely due to mineral precipitation as seen in SEM images and predicted by geochemical modeling. In experiments that emulate the caprock-reservoir boundary, final Fe (0.7ppb), an element of secondary concern for the EPA, and Pb (0.05ppb) concentrations exceed EPA limits, whereas Ba (0.140ppb), Cu (48ppb), and Zn (433ppb) values remain below EPA limits. In experiments that simulate deeper reservoir conditions, away from the caprock boundary, final Fe (3.5ppb) and Pb (0.017ppb) values indicate less mobilization than seen at the caprock-reservoir boundary, but values still exceed EPA limits. Barium concentrations always remain below the EPA limit of 2ppb, but are more readily mobilized in experiments replicating deeper reservoir conditions. In both systems, transition elements Cd, Cr, Cu, Pb and Zn behave in a similar manner, increasing in concentration with injection but continually decreasing after about 830 hours until termination of the experiment. SEM images and geochemical models indicate initial dissolution of all rocks and minerals, re-precipitation of Ca-Mg-Fe carbonates and Fe-sulfides, and precipitation of anhydrite in both systems. Calcite dissolves more readily than dolomite in these experiments, but re-precipitates in veins on dolomite. If brines leak from a storage reservoir and mix with a potable aquifer, the experimental results suggest that Ba, Cu, and Zn will not be contaminants of concern. Pb, Fe and As (still under consideration) initially exceed the EPA threshold and may require careful attention in a sequestration scenario. However, experimentally observed trends of decreasing trace metal concentration suggest that these metals could become less of a concern during the life of a carbon repository. Finally, the caprock plays an active role in trace metal mobilization in the system. The caprock provides a source of metals, although subsequent precipitation may remove metals from solution.

Carbonate component reduces o,oEDDHA/Fe sorption on two-line ferrihydrite

NASA Astrophysics Data System (ADS)

Yunta, F.; Lucena, J. J.; Smolders, E.

2012-04-01

The o,oEDDHA/Fe is the most common and effective iron chelate used as fertilizer in calcareous soils. Several authors have reported that the anionic o,oEDDHA/Fe complex is adsorbed to soil components such as ferrihydrite. The bicarbonate anion may be a competing ion for this sorption, however no studies have yet identified the extent and mechanism of this interaction. The aim of this work was to study the carbonate (bicarbonate + carbonate) effect on EDDHA/Fe adsorption on two-line ferrihydrite. Two-line ferrihydrite was synthetized adding NaOH on a nitrate iron (III) solution up to a final pH to be 8.0 and allowing to age for 22 hours at 20°C. Dialyzed ferrihydrite was characterized by determining specific parameters such as Fe/OH ratio, BET surface, point zero of charge and x-ray diffraction. The sorption was performed at three pH levels (5, 7.5 and 9.5) and three initial carbonate concentrations (from 0 to 2 mM). Initial EDDHA/Fe, ferrihydrite and ionic strength concentrations were adjusted to 0.18 mM, 10 g L-1 and 5 mM respectively. Total dissolved FeEDDHA concentrations were quantified at 480 nm. The o,oEDDHA/Fe isomers (rac-o,oEDDHA/Fe and meso-o,oEDDHA/Fe) were separated and quantified by High Performance Liquid Chromatography (HPLC) fitting a photodiode array detector (PDA). Distribution factor (KD) and sorbed o,oEDDHA/Fe concentration were determined. Actual carbonate concentration was determined using a multi N/C analyzer. Ferrihydrite samples showed a typical XRD pattern of two-line ferrihydrite, two broad peaks at about 35 and 62° respectively. The BET surfaces (two replicates) were 259.2 ± 3.1 m2/g and 256.0 ± 2.5 m2/g. The Point Zero of Salt Effect (PZSE) was 7.9 ± 0.2 as bibliographically supported for all fresh and thus not rigorously de-carbonated ferrihydrite samples. The KD of the o,oEDDHA/Fe increased from 27.4 ± 0.6 to 304 ± 6 l/kg by decreasing pH from 9.5 and 5.0 when no carbonate was added. Increasing equilibrium carbonate concentrations between 8.6 10-2 and 76 10-2 mM decreased the KD about two-fold at pH 7.5. The KD values from meso-o,oEDDHA/Fe were up to 1000 fold larger than those of rac-o,oEDDHA/Fe at highest carbonate concentration at pH 7.5 and pH dependency suggests that former binds as inner sphere whereas latter binds as outer sphere. Despite the carbonate competition is unlikely to largely affect the net sorption of the chelate in soil, clear differences between meso-o,oEDDHA/Fe and rac-o,oEDDHA/Fe sorption rate on ferrihydrite in presence of carbonate were found.

Adaptation Reactions of Siderophilic Cyanobacteria to High and Low Levels Of Environmental Iron: Implications for Biosphere History

NASA Technical Reports Server (NTRS)

Brown, I. I.; Bryant, D.; Sarkisova, S.; Shen, G.; Garrison, D.; McKay, D. S.

2009-01-01

Of all extant environments, iron-depositing hot springs may constitute the most appropriate natural models (Pierson and Parenteau, 2000) for analysis of the ecophysiology of ancient cyanobacteria (CB) which may have emerged in association with hydrothermal activity (Brown et al., 2007) and elevated levels of environmental Fe (Rouxel et al., 2005). Elevated environmental Fe2+ posed a significant challenge to the first oxygenic phototrophs - CB - because reduced Fe2+ induces toxic Fenton reactions (Wiedenheft et al., 2005). Ancient CB could have also been stressed by occasional migrations from the Fe2+-rich Ocean to the basaltic land which was almost devoid of dissolved Fe2+. That is why the study of the adaptation reactions of siderophilic CB, which inhabit iron-depositing hot springs, to up and down shifts in levels of dissolved Fe may shed light on the paleophysiology of ancient oxygenic prokaryotes. Methods. Siderophilic CB (Brown et al., 2007) were cultivated in media with different concentrations of added Fe3+. In some cases basaltic rocks were used as a source of Fe and trace elements. The processes of Fe mineralization and rock dissolution were studied using TEM, SEM and EDS techniques. Fluorescence spectroscopy was used for checking chlorophyll-protein complexes. Results. It was found that five siderophilic isolates Chroogloeocystis siderophila, JSC-1, JSC-3, JSC-11 and JSC-12 precipitated Fe-bearing phases on the exopolymeric sheaths of their cells if [Fe3+] was approx. 400-600 M (high Fe). Same [Fe3+] was most optimal one for the cultures proliferation rate (Brown et al., 2005; Brown et al., 2007). Higher concentrations of Fe3+ repressed the growth of some siderophilic CB (Brown et al., 2005). No mineralized Fe3+ was observed on the sheath of freshwater isolates Synechocystis sp. PCC 6803 and Phormidium aa. Scanning TEM in conjunction with thin-window energy dispersive X-ray spectroscopy (EDS) revealed intracellular Fe-rich phases within all three isolates studied JSC-1, JSC-3 and JSC-11. The elemental composition of the Fe-rich precipitates indicates P, Fe, and O as the major elements with minor amounts of Al and Ca. It was also found that the PSI:PSII ratio is higher in JSC-1 and JSC-3 isolates than in CB without detectable ability to mineralize Fe. SEM-EDS studies of the interaction of siderophilic cyanobacteria with Fe-rich minerals and rocks revealed, for the first time, their ability to leach ilmenite, olivine, FeS, ZnS and ferrosilicates, perhaps because the cyanobacteria studied can secrete 2-oxo-glutarate and malate which possess chelating properties. The draft of Cyanobacterium JSC-1 is currently being completed. This will help to verify the molecular mechanisms of Fe mineralization and Fe-rich minerals by siderophilic CB. Conclusions. The results obtained suggest that colloidal Fe3+ is transported in CB cytoplasm most likely through ABC-type Fe3+ transport system (Braun et al., 2004). The prevalence of PSI components over PSII in some species of siderophilic CB may indirectly support the Y. Cohen s hypothesis that PSI in cyanobacteria can be involved in Fe2+ oxidation (Cohen, 1984; 1989). The ability of siderophilic CB to mineralize Fe within their cytoplasms could be a protective survival mechanism induced by high levels of [Fe2+] and UV radiation, while the ability to leach Fe-rich minerals could have supported the expansion of ancient CB onto basaltic land.

An experimental study of ^{{{{Fe}}^{2 + } {-}{{Mg}}}} K_{{D}} between orthopyroxene and rhyolite: a strong dependence on H2O in the melt

NASA Astrophysics Data System (ADS)

Waters, Laura E.; Lange, Rebecca A.

2017-06-01

The effect of temperature, pressure, and dissolved H2O in the melt on the Fe2+-Mg exchange coefficient between orthopyroxene and rhyolite melt was investigated with a series of H2O fluid-saturated phase-equilibrium experiments. Experiments were conducted in a rapid-quench cold-seal pressure vessel over a temperature and pressure range of 785-850 °C and 80-185 MPa, respectively. Oxygen fugacity was buffered with the solid Ni-NiO assemblage in a double-capsule assembly. These experiments, when combined with H2O-undersaturated experiments in the literature, show that ^{{{{Fe}}^{2 + } {-}{{Mg}}}} K_{{D}} between orthopyroxene and rhyolite liquid increases strongly (from 0.23 to 0.54) as a function of dissolved water in the melt (from 2.7 to 5.6 wt%). There is no detectable effect of temperature or pressure over an interval of 65 °C and 100 MPa, respectively, on the Fe2+-Mg exchange coefficient values. The data show that Fe-rich orthopyroxene is favored at high water contents, whereas Mg-rich orthopyroxene crystallizes at low water contents. It is proposed that the effect of dissolved water in the melt on the composition of orthopyroxene is analogous to its effect on the composition of plagioclase. In the latter case, dissolved hydroxyl groups preferentially complex with Na+ relative to Ca2+, which reduces the activity of the albite component, leading to a more anorthite-rich (calcic) plagioclase. Similarly, it is proposed that dissolved hydroxyl groups preferentially complex with Mg2+ relative to Fe2+, thus lowering the activity of the enstatite component, leading to a more Fe-rich orthopyroxene at high water contents in the melt. The experimental results presented in this study show that reversely zoned pyroxene (i.e., Mg-rich rims) in silicic magmas may be a result of H2O degassing and not necessarily the result of mixing with a more mafic magma.

Low biodegradability of dissolved organic matter and trace metals from subarctic waters.

PubMed

Oleinikova, Olga V; Shirokova, Liudmila S; Drozdova, Olga Y; Lapitskiy, Sergey A; Pokrovsky, Oleg S

2018-03-15

The heterotrophic mineralization of dissolved organic matter (DOM) controls the CO 2 flux from the inland waters to the atmosphere, especially in the boreal waters, although the mechanisms of this process and the fate of trace metals associated with DOM remain poorly understood. We studied the interaction of culturable aquatic (Pseudomonas saponiphila) and soil (Pseudomonas aureofaciens) Gammaproteobacteria with seven different organic substrates collected in subarctic settings. These included peat leachate, pine crown throughfall, fen, humic lake, stream, river, and oligotrophic lake with variable dissolved organic carbon (DOC) concentrations (from 4 to 60mgL -1 ). The highest removal of DOC over 4days of reaction was observed in the presence of P. aureofaciens (33±5%, 43±3% and 53±7% of the initial amount in fen water, humic lake and stream, respectively). P. saponiphila degraded only 5% of DOC in fen water but did not affect all other substrates. Trace elements (TE) were essentially controlled by short-term (0-1h) adsorption on the surface of cells. Regardless of the nature of organic substrate and the identity of bacteria, the degree of adsorption ranged from 20 to 60% for iron (Fe 3+ ), 15 to 55% for aluminum (Al), 10 to 60% for manganese (Mn), 10 to 70% for nickel (Ni), 20 to 70% for copper (Cu), 10 to 60% for yttrium (Y), 30 to 80% for rare earth elements (REE), and 15 to 50% for uranium (U VI ). Rapid adsorption of organic and organo-mineral colloids on bacterial cell surfaces is novel and potentially important process, which deserves special investigation. The long-term removal of dissolved Fe and Al was generally consistent with solution supersaturation degree with respect to Fe and Al hydroxides, calculated by visual Minteq model. Overall, the biomass-normalized biodegradability of various allochthonous substrates by culturable bacteria is much lower than that of boreal DOM by natural microbial consortia. Copyright © 2017 Elsevier B.V. All rights reserved.

Bactericidal Effect of Zero-Valent Iron Nanoparticles on Escherichia coli

PubMed Central

Lee, Changha; Kim, Jee Yeon; Lee, Won Il; Nelson, Kara L.; Yoon, Jeyong; Sedlak, David L.

2008-01-01

Zero-valent iron nanoparticles (nano-Fe0) in aqueous solution rapidly inactivated Escherichia coli (E. coli). A strong bactericidal effect of nano-Fe0 was found under deaerated conditions, with a linear correlation between log inactivation and nano-Fe0 dose (0.82 log inactivation / mg/L nano-Fe0 · hr). The inactivation of E. coli under air saturation required much higher nano-Fe0 doses due to the corrosion and surface oxidation of nano-Fe0 by dissolved oxygen. Significant physical disruption of the cell membranes was observed in E. coli exposed to nano-Fe0, which may have caused the inactivation, or enhanced the biocidal effects of dissolved iron. The reaction of Fe(II) with intracellular oxygen or hydrogen peroxide also may have induced oxidative stress by producing reactive oxygen species. The bactericidal effect of nano-Fe0 was a unique property of nano-Fe0, which was not observed in other types of iron-based compounds. PMID:18678028

Variations of uranium concentrations in a multi-aquifer system under the impact of surface water-groundwater interaction

NASA Astrophysics Data System (ADS)

Wu, Ya; Li, Junxia; Wang, Yanxin; Xie, Xianjun

2018-04-01

Understanding uranium (U) mobility is vital to minimizing its concentrations in potential drinking water sources. In this study, we report spatial-seasonal variations in U speciation and concentrations in a multi-aquifer system under the impact of Sanggan River in Datong basin, northern China. Hydrochemical and H, O, Sr isotopic data, thermodynamic calculations, and geochemical modeling are used to investigate the mechanisms of surface water-groundwater mixing-induced mobilization and natural attenuation of U. In the study site, groundwater U concentrations are up to 30.2 μg/L, and exhibit strong spatial-seasonal variations that are related to pH and Eh values, as well as dissolved Ca2+, HCO3-, and Fe(III) concentrations. For the alkaline aquifers of this site (pH 7.02-8.44), U mobilization is due to the formation and desorption of Ca2UO2(CO3)30 and CaUO2(CO3)32- caused by groundwater Ca2+ elevation via mineral weathering and Na-Ca exchange, incorporated U(VI) release from calcite, and U(IV) oxidation by Fe(OH)3. U immobilization is linked to the adsorption of CaUO2(CO3)32- and UO2(CO3)34- shifted from Ca2UO2(CO3)30 because of HCO3- elevation and Ca2+ depletion, U(VI) co-precipitation with calcite, and U(VI) reduction by adsorbed Fe2+ and FeS. Those results are of great significance for the groundwater resource management of this and similar other surface water-groundwater interaction zones.

Fractionation of Fe isotopes by soil microbes and organic acids

USGS Publications Warehouse

Brantley, Susan L.; Liermann, Laura; Bullen, Thomas D.

2001-01-01

Small natural variations in Fe isotopes have been attributed to biological cycling. However, without understanding the mechanism of fractionation, it is impossible to interpret such variations. Here we show that the δ56Fe of Fe dissolved from a silicate soil mineral by siderophore-producing bacteria is as much as 0.8% lighter than bulk Fe in the mineral. A smaller isotopic shift is observed for Fe released abiotically by two chelates, and the magnitude of the shift increases with affinity of the ligand for Fe, consistent with a kinetic isotope effect during hydrolysis of Fe at the mineral surface. Fe dissolved abiotically without chelates shows no isotopic shift. The δ56Fe of the exchange fraction on soil grains is also lighter by ~0.6%-1% than Fe from both hornblende and iron oxyhydroxides. The kinetic isotope effect is therefore preserved in open systems such as soils. when recorded in the rock record, Fe isotopic fractionation could document Fe transport by organic molecules or by microbes where such entities were present in the geologic past.

Assessment of metal exposure, ecological status and required water quality monitoring strategies in small- to medium-size temperate rivers.

PubMed

Marijić, Vlatka Filipović; Perić, Mirela Sertić; Kepčija, Renata Matoničkin; Dragun, Zrinka; Kovarik, Ivana; Gulin, Vesna; Erk, Marijana

2016-01-01

The present study was undertaken to obtain a better understanding of the seasonal variability of total dissolved metal/metalloid levels and physicochemical parameters within small- to medium-size freshwater ecosystems in temperate climate region. The research was conducted in four seasons in the Sutla River, medium-size polluted, and the Črnomerec Stream, small-size unpolluted watercourse in Croatia. In the Sutla River, characterized by the rural/industrial catchment, physicochemical parameters and total dissolved metal concentrations of 21 trace and 4 macro elements were analysed downstream of the point source of pollution, the glass production facility, indicating for the first time their variability across four seasons. Based on dissolved oxygen, total dissolved solids, nutrient concentrations, conductivity and total chemical oxygen demand, quality status of the Sutla River was good, but moderate to poor during summer, what was additionally confirmed by the highest levels of the most of 25 measured metals/metalloids in summer. Comparison with the reference small-size watercourse, the Črnomerec Stream, indicated significant anthropogenic impact on the Sutla River, most evident for Fe, Mn, Mo, Ni, Pb, Rb and Tl levels (3-70-fold higher in the Sutla River across all seasons). Generally, presented results indicated significant decrease of the water quality in the anthropogenically impacted small- to medium-size watercourses in summer, regarding physicochemical water parameters and total dissolved metal/metalloid concentrations, and pointed to significant seasonality of these parameters. Confirmed seasonality of river ecological status indicates that seasonal assessment represents a prerequisite for proper classification of the water quality in small- to medium-size temperate rivers.

Iron oxidation stimulates organic matter decomposition in humid tropical forest soils.

PubMed

Hall, Steven J; Silver, Whendee L

2013-09-01

Humid tropical forests have the fastest rates of organic matter decomposition globally, which often coincide with fluctuating oxygen (O2 ) availability in surface soils. Microbial iron (Fe) reduction generates reduced iron [Fe(II)] under anaerobic conditions, which oxidizes to Fe(III) under subsequent aerobic conditions. We demonstrate that Fe (II) oxidation stimulates organic matter decomposition via two mechanisms: (i) organic matter oxidation, likely driven by reactive oxygen species; and (ii) increased dissolved organic carbon (DOC) availability, likely driven by acidification. Phenol oxidative activity increased linearly with Fe(II) concentrations (P < 0.0001, pseudo R(2)  = 0.79) in soils sampled within and among five tropical forest sites. A similar pattern occurred in the absence of soil, suggesting an abiotic driver of this reaction. No phenol oxidative activity occurred in soils under anaerobic conditions, implying the importance of oxidants such as O2 or hydrogen peroxide (H2 O2 ) in addition to Fe(II). Reactions between Fe(II) and H2 O2 generate hydroxyl radical, a strong nonselective oxidant of organic compounds. We found increasing consumption of H2 O2 as soil Fe(II) concentrations increased, suggesting that reactive oxygen species produced by Fe(II) oxidation explained variation in phenol oxidative activity among samples. Amending soils with Fe(II) at field concentrations stimulated short-term C mineralization by up to 270%, likely via a second mechanism. Oxidation of Fe(II) drove a decrease in pH and a monotonic increase in DOC; a decline of two pH units doubled DOC, likely stimulating microbial respiration. We obtained similar results by manipulating soil acidity independently of Fe(II), implying that Fe(II) oxidation affected C substrate availability via pH fluctuations, in addition to producing reactive oxygen species. Iron oxidation coupled to organic matter decomposition contributes to rapid rates of C cycling across humid tropical forests in spite of periodic O2 limitation, and may help explain the rapid turnover of complex C molecules in these soils. © 2013 John Wiley & Sons Ltd.

Fe-C-S systematics in Bengal Fan sediments

NASA Astrophysics Data System (ADS)

Volvoikar, S. P.; Mazumdar, A.; Goswami, H.; Pujari, S.; Peketi, A.

2017-12-01

Global biogeochemical cycles of iron, carbon and sulfur (Fe-C-S) are interrelated. Sulfate reduction in marine sediments is the major factor controlling the cycling and burial of carbon, sulfur and iron. Organoclastic sulfate reduction and anaerobic oxidation of methane (AOM) are the two main processes responsible for sulfate reduction in marine sediments. The amount and reactivity of organic matter, iron minerals and concentrations of dissolved sulfide in pore water control the burial of iron sulfide and organic bound sulfur in marine sediments. Here we investigate the sulfidization process in a sediment core from the western part of upper Bay of Bengal fan characterized by efficient burial of organic matter with siliclastic load. A 30 m long sediment core (MD 161/29, Lat. 170 18.04' N, Long. 870 22.56' E, water depth: 2434m) was collected onboard Marion Dufresne (May, 2007) and studied for Fe-S speciation and organic matter characterization. Buffered dithionite extractable iron (FeD) varies from 0.71 to 1.43 wt % (Avg. 0.79 wt %). FeD represents Fe oxides and oxyhydroxides mainly, ferrihydrite, lepidocrocite, goethite and hematite. Acid volatile sulfur (AVS) varies from 0.0015 to 0.63 wt % (avg: 0.058 wt %), while chromium reducible sulfur (CRS) varies from 0.00047 to 0.29 wt % (avg. 0.054 wt %). Based on the vertical distribution patterns of FeD, AVS and CRS, the core is divided into three zones, the lower (3000 to 1833 cm), middle (1833 to 398 cm) and upper (398 cm to surface) zones. FeD shows higher concentration in the lower zone. FeTR (FeOx + FeD + FeCRS + FeAVS) also exhibit higher concentration in this zone, suggesting higher availability of reactive iron for iron sulfide precipitation. AVS, elemental sulfur, spikes of CRS and gradual enrichment of δ34SAVS and δ34SCRS with sharp peaks in-between is noted in the lower zone. The gradual enrichment of δ34SAVS and δ34SCRS is the outcome of late diagenetic pyritization with higher availability of sulfide (HS- and H2S) from AOM.

Fe hydroxyphosphate precipitation and Fe(II) oxidation kinetics upon aeration of Fe(II) and phosphate-containing synthetic and natural solutions

NASA Astrophysics Data System (ADS)

van der Grift, B.; Behrends, T.; Osté, L. A.; Schot, P. P.; Wassen, M. J.; Griffioen, J.

2016-08-01

Exfiltration of anoxic Fe-rich groundwater into surface water and the concomitant oxidative precipitation of Fe are important processes controlling the transport of phosphate (PO4) from agricultural areas to aquatic systems. Here, we explored the relationship between solution composition, reaction kinetics, and the characteristics of the produced Fe hydroxyphosphate precipitates in a series of aeration experiments with anoxic synthetic water and natural groundwater. A pH stat device was used to maintain constant pH and to record the H+ production during Fe(II) oxidation in the aeration experiments in which the initial aqueous P/Fe ratios ((P/Fe)ini), oxygen concentration and pH were varied. In general, Fe(II) oxidation proceeded slower in the presence of PO4 but the decrease of the PO4 concentration during Fe(II) oxidation due to the formation of Fe hydroxyphosphates caused additional deceleration of the reaction rate. The progress of the reaction could be described using a pseudo-second-order rate law with first-order dependencies on PO4 and Fe(II) concentrations. After PO4 depletion, the Fe(II) oxidation rates increased again and the kinetics followed a pseudo-first-order rate law. The first-order rate constants after PO4 depletion, however, were lower compared to the Fe(II) oxidation in a PO4-free solution. Hence, the initially formed Fe hydroxyphosphates also affect the kinetics of continuing Fe(II) oxidation after PO4 depletion. Presence of aqueous PO4 during oxidation of Fe(II) led to the formation of Fe hydroxyphosphates. The P/Fe ratios of the precipitates ((P/Fe)ppt) and the recorded ratio of H+ production over decrease in dissolved Fe(II) did not change detectably throughout the reaction despite a changing P/Fe ratio in the solution. When (P/Fe)ini was 0.9, precipitates with a (P/Fe)ppt ratio of about 0.6 were formed. In experiments with (P/Fe)ini ratios below 0.6, the (P/Fe)ppt decreased with decreasing (P/Fe)ini and pH value. Aeration experiments with natural groundwater showed no principal differences in Fe(II) oxidation kinetics and in PO4 immobilisation dynamics compared with synthetic solutions with corresponding P/Fe ratio, pH and oxygen pressure. However, aeration of groundwater with relative high DOC concentrations and a low salinity lead to P-rich Fe colloids that were colloidally stable. The formation of a Fe hydroxyphosphate phase with a molar P/Fe ratio of 0.6 can be used for predictive modelling of PO4 immobilisation upon aeration of pH-neutral natural groundwater with an (P/Fe)ini ratio up to 1.5. These findings provide a solid basis for further studies on transport and bioavailability of phosphorus in streams, ditches and channels that receive anoxic Fe-rich groundwater.

Weathering of the Rio Blanco quartz diorite, Luquillo Mountains, Puerto Rico: Coupling oxidation, dissolution, and fracturing

USGS Publications Warehouse

Buss, H.L.; Sak, P.B.; Webb, S.M.; Brantley, S.L.

2008-01-01

In the mountainous Rio Icacos watershed in northeastern Puerto Rico, quartz diorite bedrock weathers spheroidally, producing a 0.2-2 m thick zone of partially weathered rock layers (???2.5 cm thickness each) called rindlets, which form concentric layers around corestones. Spheroidal fracturing has been modeled to occur when a weathering reaction with a positive ??V of reaction builds up elastic strain energy. The rates of spheroidal fracturing and saprolite formation are therefore controlled by the rate of the weathering reaction. Chemical, petrographic, and spectroscopic evidence demonstrates that biotite oxidation is the most likely fracture-inducing reaction. This reaction occurs with an expansion in d (0 0 1) from 10.0 to 10.5 A??, forming 'altered biotite'. Progressive biotite oxidation across the rindlet zone was inferred from thin sections and gradients in K and Fe(II). Using the gradient in Fe(II) and constraints based on cosmogenic age dates, we calculated a biotite oxidation reaction rate of 8.2 ?? 10-14 mol biotite m-2 s-1. Biotite oxidation was documented within the bedrock corestone by synchrotron X-ray microprobe fluorescence imaging and XANES. X-ray microprobe images of Fe(II) and Fe(III) at 2 ??m resolution revealed that oxidized zones within individual biotite crystals are the first evidence of alteration of the otherwise unaltered corestone. Fluids entering along fractures lead to the dissolution of plagioclase within the rindlet zone. Within 7 cm surrounding the rindlet-saprolite interface, hornblende dissolves to completion at a rate of 6.3 ?? 10-13 mol hornblende m-2 s-1: the fastest reported rate of hornblende weathering in the field. This rate is consistent with laboratory-derived hornblende dissolution rates. By revealing the coupling of these mineral weathering reactions to fracturing and porosity formation we are able to describe the process by which the quartz diorite bedrock disaggregates and forms saprolite. In the corestone, biotite oxidation induces spheroidal fracturing, facilitating the influx of fluids that react with other minerals, dissolving plagioclase and chlorite, creating additional porosity, and eventually dissolving hornblende and precipitating secondary minerals. The thickness of the resultant saprolite is maintained at steady state by a positive feedback between the denudation rate and the weathering advance rate driven by the concentration of pore water O2 at the bedrock-saprolite interface. ?? 2008 Elsevier Ltd. All rights reserved.

Dominance of cyanobacterial and cryptophytic assemblage correlated to CDOM at heavy metal contamination sites of Gujarat, India.

PubMed

Patidar, Shailesh Kumar; Chokshi, Kaumeel; George, Basil; Bhattacharya, Sourish; Mishra, Sandhya

2015-01-01

Industrial clusters of Gujarat, India, generate high quantity of effluents which are received by aquatic bodies such as estuary and coastal water. In the present study, microalgal assemblage, heavy metals, and physico-chemical variables were studied from different habitats. Principal component analysis revealed that biovolume of cyanobacterial and cryptophytic community positively correlated with the heavy metal concentration (Hg, As, Zn, Fe, Mo, Ni, and Co) and chromophoric dissolved organic matter (CDOM) under hypoxic environment. Green algae and diatoms dominated at comparatively lower nitrate concentration which was positively associated with Pb and Mn.

Performance and microbial community analysis of bio-electrocoagulation on simultaneous nitrification and denitrification in submerged membrane bioreactor at limited dissolved oxygen.

PubMed

Li, Liang; Dong, Yihua; Qian, Guangsheng; Hu, Xiaomin; Ye, Linlin

2018-06-01

A pair of Fe-C electrodes was installed in a traditional submerged membrane bioreactor (MBR, Rc), and a novel asynchronous periodic reversal bio-electrocoagulation system (Re) was developed. The simultaneous nitrification and denitrification (SND) performance was discussed under limited dissolved oxygen (DO). Results showed that electrocoagulation enhanced total nitrogen (TN) removal from 59.48% to 75.09% at 1.2 mg/L DO. Additionally, Fe electrode could increase sludge concentration, particle size, and enzyme activities related to nitrogen removal. The enzyme activities of Hydroxylamine oxidoreductase (HAO), Nitrate Reductase (NAR), nitric oxide reductase NOR and nitrous oxide reductase (N 2 OR) in Re were 38.35%, 21.59%, 89.96% and 38.64% higher than Rc, respectively. Moreover, electrocoagulation was advantageous for nitrite accumulation, indicating partial nitrification and denitrification were more easily achieved in Re. Besides, results from high throughput sequencing analysis revealed that electrocoagulation increased the relative abundance of most genera related to nitrogen removal, including Nitrosomonas, Comamonadaceae_unclassified, Haliangium and Denitratisoma. Copyright © 2018 Elsevier Ltd. All rights reserved.

Influence of Oxalate on Ni Fate during Fe(II)-Catalyzed Recrystallization of Hematite and Goethite.

PubMed

Flynn, Elaine D; Catalano, Jeffrey G

2018-06-05

During biogeochemical iron cycling at redox interfaces, dissolved Fe(II) induces the recrystallization of Fe(III) oxides. Oxalate and other organic acids promote dissolution of these minerals and may also induce recrystallization. These processes may redistribute trace metals among the mineral bulk, mineral surface, and aqueous solution. However, the impact of interactions among organic acids, dissolved Fe(II), and iron oxide minerals on trace metal fate in such systems is unclear. The present study thus explores the effect of oxalate on Ni release from and incorporation into hematite and goethite in the absence and presence of Fe(II). When Ni is initially structurally incorporated into the iron oxides, both oxalate and dissolved Fe(II) promote the release of Ni to aqueous solution. When both species are present, their effects on Ni release are synergistic at pH 7 but inhibitory at pH 4, indicating that cooperative and competitive interactions vary with pH. In contrast, oxalate suppresses Ni incorporation into goethite and hematite during Fe(II)-induced recrystallization, decreasing the proportion of Ni substituting in a mineral structure by up to 36%. These observations suggest that at redox interfaces oxalate largely enhances trace metal mobility. In such settings, oxalate, and likely other organic acids, may thus enhance micronutrient availability and inhibit contaminant sequestration.

Benzyl and Methyl Fatty Hydroxamic Acids Based on Palm Kernel Oil as Chelating Agent for Liquid-Liquid Iron(III) Extraction

PubMed Central

Haron, Md Jelas; Jahangirian, Hossein; Silong, Sidik; Yusof, Nor Azah; Kassim, Anuar; Rafiee-Moghaddam, Roshanak; Mahdavi, Behnam; Peyda, Mazyar; Abdollahi, Yadollah; Amin, Jamileh

2012-01-01

Liquid-liquid iron(III) extraction was investigated using benzyl fatty hydroxamic acids (BFHAs) and methyl fatty hydroxamic acids (MFHAs) as chelating agents through the formation of iron(III) methyl fatty hydroxamate (Fe-MFHs) or iron(III) benzyl fatty hydroxamate (Fe-BFHs) in the organic phase. The results obtained under optimized conditions, showed that the chelating agents in hexane extract iron(III) at pH 1.9 were realized effectively with a high percentage of extraction (97.2% and 98.1% for MFHAs and BFHAs, respectively). The presence of a large amount of Mg(II), Ni(II), Al(III), Mn(II) and Co(II) ions did affect the iron(III) extraction. Finally stripping studies for recovering iron(III) from organic phase (Fe-MFHs or Fe-BFHs dissolved in hexane) were carried out at various concentrations of HCl, HNO3 and H2SO4. The results showed that the desired acid for recovery of iron(III) was 5 M HCl and quantitative recovery of iron(III) was achieved from Fe(III)-MFHs and Fe(III)-BFHs solutions in hexane containing 5 mg/L of Fe(III). PMID:22408444

Environmental effects on the aquatic system and metal discharge to the Mediterranean Sea from a near-neutral zinc-ferrous sulfate mine drainage

USGS Publications Warehouse

Frau, Franco; Medas, Daniela; Da Pelo, Stefania; Wanty, Richard B.; Cidu, Rosa

2015-01-01

After mine closure in the 1980s and subsequent shutdown of the dewatering system, groundwater rebound led to drainage outflow from the Casargiu gallery (Montevecchio mine, SW Sardinia, Italy) beginning in 1997. Mine drainage had pH 6.0 and dissolved concentrations of sulfate (5000 mg/L) and metals (e.g., 1000 mg/L Zn, 230 mg/L Fe, 150 mg/L Mn) much higher than those previously measured in groundwater under dewatering conditions. As compared with the first stages of rebound at Casargiu, a very high contamination level still persists after more than 15 years of flushing. Mine drainage (20–70 L/s; pH 6.0 ± 0.2; Zn-Mg-Ca-SO4 composition) flowed into the Rio Irvi. Abundant precipitation of amorphous Fe(III)-(oxy)hydroxides occurred. Moreover, sulfate-bearing green rust was observed to flocculate in the reach of the Rio Irvi where pH was still circumneutral. Water sampling along this stream for about 6 km almost to its mouth in the Mediterranean Sea showed a pH decrease from 6.0 to 4.0 and a significant removal of Fe (46 %) and As (96 %), while sulfate, Zn, Mn, Co, Ni, and Cd showed small variations downstream. Lead was initially adsorbed onto Fe(III)-(oxy)hydroxides, then desorbed as pH dropped below 5. The estimated amount of dissolved metals discharged into the Mediterranean Sea is significant (e.g., 900 kg/day Zn, 1.4 kg/day Cd, 5 kg/day Ni). In particular, a conservative estimation of the amount of Zn discharged to the sea is about 330 ton/year, which would correspond to 1.4 % of the global annual flux of dissolved Zn from uncontaminated rivers to the oceans.

Building Towards a Conceptual Model for Phosphorus Transport in Lowland Catchments

NASA Astrophysics Data System (ADS)

van der Grift, B.; Griffioen, J.; Oste, L.

2016-12-01

The release of P to surface water following P leaching from heavily fertilized agricultural fields to groundwater and the extent of P retention at the redox interphase are of major importance for surface water quality. We studied the role of biogeochemical and hydrological processes during exfiltration of groundwater and their impact on phosphorus transport in lowland catchments in the Netherlands. Our study showed that the mobility and ecological impact of P in surface waters in lowland catchments or polders like in the Netherlands is strongly controlled by the exfiltration of anoxic groundwater containing ferrous iron. Chemical precipitates derived from groundwater-associated Fe(II) seeping into the overlying surface water contribute to immobilization of dissolved phosphate and, therefore, reduces its bioavailability. Aeration experiments with Fe(II) and phosphate-containing synthetic solutions and natural groundwater showed that Fe(II) oxidation in presence of phosphate leads initially to formation of Fe(III) hydroxyphosphates precipitates until phosphate is near-depleted from solution. A field campaign on P specation in surface waters draining agricultural land showed, additionally, that the total-P concentration is strongly dominated by iron-bound. Between 75 and 95% of the total-P concentration in the water samples was iron-bound particulate P. After the turnover of dissolved P to iron-bound particulate P, the P transport in catchments or polders is controlled by sedimentation and erosion of suspended sediments in the water body. Shear flow-induced surface erosion of sediment beds upon natural discharge events or generated by pumping stations is thus an important mechanism for P transport in catchments or polders. The flow velocities in headwaters like drainage ditches are generally low and not high enough to cause a bed shear stress that exceed the critical shear stress. Transport of particulate P that originates from groundwater and (agricultural) drains discharge is strongly retained but particulate P can be remobilized due to biogeochemical processes in the sediment layer at other moments. This makes it difficult to link agricultural practice to P concentrations in the surface water and this should be accounted for when judging measures to reduce P loads from agriculture.

Chalcopyrite dissolution: Scanning photoelectron microscopy examination of the evolution of sulfur species with and without added iron or pyrite

NASA Astrophysics Data System (ADS)

Li, Yubiao; Qian, Gujie; Brown, Paul L.; Gerson, Andrea R.

2017-09-01

Dissolution and oxidation of sulfide minerals play key roles in both acid and metalliferous rock drainage and supergene enrichment. Surface speciation heterogeneity, critical to understanding mechanisms of mineral sulfide dissolution, has to date largely not been considered. To this end synchrotron scanning photoelectron microscopy (SPEM) was employed to examine freshly fractured and partially dissolved chalcopyrite (CuFeS2) surfaces (pH 1.0 HClO4 solution, redox potential 650 mV relative to a standard hydrogen electrode, 75 °C). S2- (bulk), S22- and Sn2- were found to be present on all samples at varying concentrations. Oxidation was observed to take place heterogeneously at the sub-micron scale. As compared to chalcopyrite partially dissolved for 5 days, extended dissolution to 10 days did not show appreciably enhanced oxidation of surface species; however surface roughness increased markedly due to the growth/overlap of oxidised sulfur species. On addition of 4 mM iron both S0 and SO42- were observed but not SO32-, indicating that the greater Fe3+ activity/concentration promotes heterogeneous sulfur oxidation. On contact of pyrite (FeS2) with chalcopyrite, significantly greater chalcopyrite surface oxidation was observed than for the other systems examined, with S0, SO32- and SO42- being identified heterogeneously across the surface. It is proposed that chalcopyrite oxidative dissolution is enhanced by increasing its cathodic area, e.g. contacting with pyrite, while increased Fe3+ activity/concentration also contributes to increased dissolution rates. The high degree of surface heterogeneity of these surface products indicates that these surfaces are not passivated by their formation. These results suggest that chalcopyrite dissolution will be accelerated when in contact with pyrite at solution redox potential intermediate between the rest potentials of chalcopyrite and pyrite (560 mV and 660 mV, respectively) and/or iron rich acidic waters with resulting enhanced formation of secondary sulfur containing species and release of copper and iron. This in turn suggests accelerated supergene formation and enhanced metalliferous drainage under these conditions.

Natural decrease of dissolved arsenic in a small stream receiving drainages of abandoned silver mines in Guanajuato, Mexico.

PubMed

Arroyo, Yann Rene Ramos; Muñoz, Alma Hortensia Serafín; Barrientos, Eunice Yanez; Huerta, Irais Rodriguez; Wrobel, Kazimierz; Wrobel, Katarzyna

2013-11-01

Arsenic release from the abandoned mines and its fate in a local stream were studied. Physicochemical parameters, metals/metalloids and arsenic species were determined. One of the mine drainages was found as a point source of contamination with 309 μg L(-1) of dissolved arsenic; this concentration declined rapidly to 10.5 μg L(-1) about 2 km downstream. Data analysis confirmed that oxidation of As(III) released from the primary sulfide minerals was favored by the increase of pH and oxidation reduction potential; the results obtained in multivariate approach indicated that self-purification of water was due to association of As(V) with secondary solid phase containing Fe, Mn, Ca.

Organic and inorganic carbon dynamics in a karst aquifer: Santa Fe River Sink-Rise system, north Florida, USA

NASA Astrophysics Data System (ADS)

Jin, Jin; Zimmerman, Andrew R.; Moore, Paul J.; Martin, Jonathan B.

2014-03-01

Spatiotemporal variations in dissolved organic carbon (DOC), dissolved inorganic carbon (DIC), major ions concentrations and other geochemical parameters including stable carbon isotopes of DIC (δ13CDIC), were measured in surface water and deep and shallow well water samples of the Santa Fe River Sink-Rise eogenetic karst system, north Florida, USA. Three end-member water sources were identified: one DOC-rich/DIC-poor/δ13CDIC-depleted, one DOC-poor/DIC-rich/δ13CDIC-enriched, and one enriched in major ions. Given their spatiotemporal distributions, they were presumed to represent soil water, upper aquifer groundwater, and deep aquifer water sources, respectively. Using assumed ratios of Na+, Cl, and SO42- for each end-member, a mixing model calculated the contribution of each water source to each sample. Then, chemical effects of biogeochemical reactions were calculated as the difference between those predicted by the mixing model and measured species concentrations. In general, carbonate mineral dissolution occurred throughout the Sink-Rise system, surface waters were net autotrophic and the subsurface was in metabolic balance, i.e., no net DOC or DIC production or consumption. However, there was evidence for chemolithoautotrophy, perhaps by hydrogen oxidizing microbes, at some deep aquifer sites. Mineralization of this autochthonous natural dissolved organic matter (NDOM) led to localized carbonate dissolution as did surface water-derived NDOM supplied to shallow well sites during the highest flow periods. This study demonstrates linkages between hydrology, abiotic and microbial processes and carbon dynamics and has important implications for groundwater quality, karst morphologic evolution, and hydrogeologic projects such as aquifer storage and recovery in karst systems.

Diel changes in water chemistry in an arsenic-rich stream and treatment-pond system

USGS Publications Warehouse

Gammons, C.H.; Grant, T.M.; Nimick, D.A.; Parker, S.R.; DeGrandpre, M.D.

2007-01-01

Arsenic concentrations are elevated in surface waters of the Warm Springs Ponds Operable Unit (WSPOU), located at the head of the upper Clark Fork River Superfund site, Montana, USA. Arsenic is derived from historical deposition of smelter emissions (Mill and Willow Creeks) and historical mining and milling wastes (Silver Bow Creek). Although long-term monitoring has characterized the general seasonal and flow-related trends in As concentrations in these streams and the pond system used to treat Silver Bow Creek water, little is known about solubility controls and sorption processes that influence diel cycles in As concentrations. Diel (24-h) sampling was conducted in July 2004 and August 2005 at the outlet of the treatment ponds, at two locations along a nearby reconstructed stream channel that diverts tributary water around the ponds, and at Silver Bow Creek 2??km below the ponds. Dissolved As concentration increased up to 51% during the day at most of the stream sites, whereas little or no diel change was displayed at the treatment-pond outlet. The strong cycle in streams is explained by pH- and temperature-dependent sorption of As onto hydrous metal oxides or biofilms on the streambed. Concentrations of dissolved Ca2+ and HCO3- at the stream sites showed a diel temporal pattern opposite to that of As, and geochemical modeling supports the hypothesis that the concentrations of Ca2+ and HCO3- were controlled by precipitation of calcite during the warm afternoon hours when pH rose above 9.0. Nightly increases in dissolved Mn and Fe(II) concentrations were out of phase with concentrations of other divalent cations and are more likely explained by redox phenomena. ?? 2007 Elsevier B.V. All rights reserved.

Ferrous and ferric ion generation during iron electrocoagulation.

PubMed

Lakshmanan, Divagar; Clifford, Dennis A; Samanta, Gautam

2009-05-15

Our research on arsenate removal by iron electrocoagulation (EC) produced highly variable results, which appeared to be due to Fe2+ generation without subsequent oxidation to Fe3+. Because the environmental technology literature is contradictory with regard to the generation of ferric or ferrous ions during EC, the objective of this research was to establish the iron species generated during EC with iron anodes. Experimental results demonstrated that Fe2+, not Fe3+, was produced at the iron anode. Theoretical current efficiency was attained based on Fe2+ production with a clean iron rod, regardless of current, dissolved-oxygen (DO) level, or pH (6.5-8.5). The Fe2+ remaining after generation and mixing decreased with increasing pH and DO concentration due to rapid oxidation to Fe3+. At pH 8.5, Fe2+ was completely oxidized, which resulted in the desired Fe(OH)3(s)/ FeOOH(s), whereas, at pH 6.5 and 7.5, incomplete oxidation was observed, resulting in a mixture of soluble Fe2+ and insoluble Fe(OH)3(s)/FeOOH(s). When compared with Fe2+ chemical coagulation, a transient pH increase during EC led to faster Fe2+ oxidation. In summary, for EC in the pH 6.5-7.5 range and at low DO conditions, there is a likelihood of soluble Fe2+ species passing through a subsequentfiltration process resulting in secondary contamination and inefficient contaminant removals.

Combining cross flow ultrafiltration and diffusion gradients in thin-films approaches to determine trace metal speciation in freshwaters

NASA Astrophysics Data System (ADS)

Liu, Ruixia; Lead, Jamie R.; Zhang, Hao

2013-05-01

Cross flow ultrafiltration (CFUF) and diffusive gradients in thin films (DGT) with open pore gel (OP) and restricted pore gel (RP) were used to measure trace metal speciation in selected UK freshwaters. The proportions of metals present in particulate forms (>1 μm) varied widely between 40-85% Pb, 60-80% Al, 7-56% Mn, 10-49% Cu, 0-55% Zn, 20-38% Cr, 20-30% Fe, 6-25% Co, 5-22% Cd and <7% Ni. In the colloidal fraction (2 kDa-1 μm) values varied between 53-91% Pb, 33-55% Al, 21-55% Cu, 20-44% Fe, 34-36% Cr, 20-40% Cd, 7-28% Co and Ni, 2-32% Zn and <8% Mn. Wide variations were also observed in the ultrafiltered fraction (<2 kDa). These results indicated that colloids indeed influenced the occurrence and transport of Al, Fe, Cr, Co, Ni, Cu, Zn, Cr and Pb metals in rivers, while inorganic or organic colloids did not exert an important control on Mn transport in the selected freshwaters. Of total species, total labile metal measured by DGT-OP accounted for 1.4-50% for Al, Fe, Co, Ni, Cu, Cd and Pb in all selected waters. Of these metals total labile Pb concentration was the lowest with value less than 1.4% although this value slightly increased after deducting particulate fractions. In some waters, a majority of total Mn, Zn and Cr is DGT labile, in which the DGT labile Mn fraction accounted for 98-118% of the total dissolved phase. In most cases, the inorganic labile concentration measured by DGT-RP was lower than the total labile metal concentration. By the combination of CFUF and DGT techniques, the concentrations of total labile and inorganic labile metal species in CFUF-derived truly dissolved phase were measured in four water samples. 100% of ultrafiltered Mn species was found to be total DGT labile. The proportions of total labile metal species were lower than those of ultrafiltered fraction for Al, Fe, Co, Ni, Cu, Cd and Pb in all selected waters, and Cr and Zn in some cases, indicating a large amount of natural complexing ligands with smaller size for the metals to form kinetically inert species or thermodynamically stable complexes. Observed discrepancies in metal speciation between metals and within sampling sites were related to the differences in the characteristics of the metals and the nature of water sources.

Uranium biogeochemistry across the redox transition zone of a permanently stratified fjord: Framvaren, Norway

USGS Publications Warehouse

Swarzenski, P.W.; McKee, B.A.; Skei, J.M.; Todd, J.F.

1999-01-01

During August 1995, the vertical concentration profile of dissolved and particulate uranium exhibited strong non-conservative characteristics in the upper 30 m of Framvaren Fjord. There was a pronounced peak in both particulate (> 0.2 ??m; 1.09 nM) and dissolved (< 0.2 ??m; 17.06 nM) uranium in the finely stratified waters at the O2/H2S interface which is positioned well within the euphotic zone at about 20-21 m. Such concentration maxima at the redox boundary are also observed for dissolved organic carbon (DEC), Sr and Ba. Dissolved U levels seen in the water column from 18 m down to 30 m exceeded the high salinity (salinity = 35) U concentrations (13.63 ?? 0.84 nM; Chen, J.H., Edwards, R.L., Wasserburg, G.L., 1986. 238U, 234U and 232Th in seawater. Earth Planet Sci. Lett. 80, 241-251.) observed uniformly in the open ocean. A prolific population of S microbes (e.g., Chromatium, Chlorobium sp.) flourishes at the O2/H2S interface. The source of elevated U at the redox boundary must be due to microbial uptake and subsequent release processes rather than dilution from oceanic uranium. Uranium oxidation state determinations in waters from 1, 22 and 30 m depth reveal that reduced U(IV) is not present in significant abundance, and that the chemical and/or biological reduction of hexavalent uranium is largely inhibited. Our results suggest that U and other trace constituents such as DOC, Sr, Ba, Fe(II), Mn(II) are greatly modified by direct and indirect microbial transformation reactions which are most concentrated across the redox transition zone in Framvaren Fjord.

Arsenic removal with iron(II) and iron(III) in waters with high silicate and phosphate concentrations.

PubMed

Roberts, Linda C; Hug, Stephan J; Ruettimann, Thomas; Billah, Morsaline; Khan, Abdul Wahab; Rahman, Mohammad Tariqur

2004-01-01

Arsenic removal by passive treatment, in which naturally present Fe(II) is oxidized by aeration and the forming iron(III) (hydr)oxides precipitate with adsorbed arsenic, is the simplest conceivable water treatment option. However, competing anions and low iron concentrations often require additional iron. Application of Fe(II) instead of the usually applied Fe(III) is shown to be advantageous, as oxidation of Fe(II) by dissolved oxygen causes partial oxidation of As(III) and iron(III) (hydr)oxides formed from Fe(II) have higher sorption capacities. In simulated groundwater (8.2 mM HCO3(-), 2.5 mM Ca2+, 1.6 mM Mg2+, 30 mg/L Si, 3 mg/L P, 500 ppb As(III), or As(V), pH 7.0 +/- 0.1), addition of Fe(II) clearly leads to better As removal than Fe(III). Multiple additions of Fe(II) further improved the removal of As(II). A competitive coprecipitation model that considers As(III) oxidation explains the observed results and allows the estimation of arsenic removal under different conditions. Lowering 500 microg/L As(III) to below 50 microg/L As(tot) in filtered water required > 80 mg/L Fe(III), 50-55 mg/L Fe(II) in one single addition, and 20-25 mg/L in multiple additions. With As(V), 10-12 mg/L Fe(II) and 15-18 mg/L Fe(III) was required. In the absence of Si and P, removal efficiencies for Fe(II) and Fe(III) were similar: 30-40 mg/L was required for As(II), and 2.0-2.5 mg/L was required for As(V). In a field study with 22 tubewells in Bangladesh, passive treatment efficiently removed phosphate, but iron contents were generally too low for efficient arsenic removal.

Flow and sorption controls of groundwater arsenic in individual boreholes from bedrock aquifers in central Maine, USA

USGS Publications Warehouse

Yang, Qiang; Culbertson, Charles W.; Nielsen, Martha G.; Schalk, Charles W.; Johnson, Carole D.; Marvinney, Robert G.; Stute, Martin; Zheng, Yan

2014-01-01

To understand the hydrogeochemical processes regulating well water arsenic (As) evolution in fractured bedrock aquifers, three domestic wells with [As] up to 478 μg/L are investigated in central Maine. Geophysical logging reveals that fractures near the borehole bottom contribute 70-100% of flow. Borehole and fracture water samples from various depths show significant proportions of As (up to 69%) and Fe (93-99%) in particulates (>0.45 μm). These particulates and those settled after a 16-day batch experiment contain 560-13,000 g/kg of As and 14-35% weight/weight of Fe. As/Fe ratios (2.5-20 mmol/mol) and As partitioning ratios (adsorbed/dissolved [As], 20,000-100,000 L/kg) suggest that As is sorbed onto amorphous hydrous ferric oxides. Newly drilled cores also show enrichment of As (up to 1300 mg/kg) sorbed onto secondary iron minerals on the fracture surfaces. Pumping at high flow rates induces large decreases in particulate As and Fe, a moderate increase in dissolved [As] and As(III)/As ratio, while little change in major ion chemistry. The δD and δ18O are similar for the borehole and fracture waters, suggesting a same source of recharge from atmospheric precipitation. Results support a conceptual model invoking flow and sorption controls on groundwater [As] in fractured bedrock aquifers whereby oxygen infiltration promotes the oxidation of As-bearing sulfides at shallower depths in the oxic portion of the flow path releasing As and Fe; followed by Fe oxidation to form Fe oxyhydroxide particulates, which are transported in fractures and sorb As along the flow path until intercepted by boreholes. In the anoxic portions of the flow path, reductive dissolution of As-sorbed iron particulates could re-mobilize As. For exposure assessment, we recommend sampling of groundwater without filtration to obtain total As concentration in groundwater.

Flow and sorption controls of groundwater arsenic in individual boreholes from bedrock aquifers in central Maine, USA.

PubMed

Yang, Qiang; Culbertson, Charles W; Nielsen, Martha G; Schalk, Charles W; Johnson, Carole D; Marvinney, Robert G; Stute, Martin; Zheng, Yan

2015-02-01

To understand the hydrogeochemical processes regulating well water arsenic (As) evolution in fractured bedrock aquifers, three domestic wells with [As] up to 478 μg/L are investigated in central Maine. Geophysical logging reveals that fractures near the borehole bottom contribute 70-100% of flow. Borehole and fracture water samples from various depths show significant proportions of As (up to 69%) and Fe (93-99%) in particulates (>0.45 μm). These particulates and those settled after a 16-day batch experiment contain 560-13,000 mg/kg of As and 14-35% weight/weight of Fe. As/Fe ratios (2.5-20 mmol/mol) and As partitioning ratios (adsorbed/dissolved [As], 20,000-100,000 L/kg) suggest that As is sorbed onto amorphous hydrous ferric oxides. Newly drilled cores also show enrichment of As (up to 1300 mg/kg) sorbed onto secondary iron minerals on the fracture surfaces. Pumping at high flow rates induces large decreases in particulate As and Fe, a moderate increase in dissolved [As] and As(III)/As ratio, while little change in major ion chemistry. The δD and δ(18)O are similar for the borehole and fracture waters, suggesting a same source of recharge from atmospheric precipitation. Results support a conceptual model invoking flow and sorption controls on groundwater [As] in fractured bedrock aquifers whereby oxygen infiltration promotes the oxidation of As-bearing sulfides at shallower depths in the oxic portion of the flow path releasing As and Fe; followed by Fe oxidation to form Fe oxyhydroxide particulates, which are transported in fractures and sorb As along the flow path until intercepted by boreholes. In the anoxic portions of the flow path, reductive dissolution of As-sorbed iron particulates could re-mobilize As. For exposure assessment, we recommend sampling of groundwater without filtration to obtain total As concentration in groundwater. Copyright © 2014 Elsevier B.V. All rights reserved.

Flow and sorption controls of groundwater arsenic in individual boreholes from bedrock aquifers in central Maine, USA

PubMed Central

Yang, Qiang; Culbertson, Charles W.; Nielsen, Martha G.; Schalk, Charles W.; Johnson, Carole D.; Marvinney, Robert G.; Stute, Martin; Zheng, Yan

2014-01-01

To understand the hydrogeochemical processes regulating well water arsenic (As) evolution in fractured bedrock aquifers, three domestic wells with [As] up to 478 µg/L are investigated in central Maine. Geophysical logging reveals that fractures near the borehole bottom contribute 70–100% of flow. Borehole and fracture water samples from various depths show significant proportions of As (up to 69%) and Fe (93–99%) in particulates (>0.45 µm). These particulates and those settled after a 16-day batch experiment contain 560–13,000 mg/kg of As and 14–35% weight/weight of Fe. As/Fe ratios (2.5–20 mmole/mole) and As partitioning ratios (adsorbed/dissolved [As], 20,000–100,000 L/kg) suggest that As is sorbed onto amorphous hydrous ferric oxides. Newly drilled cores also show enrichment of As (up to 1,300 mg/kg) sorbed onto secondary iron minerals on the fracture surfaces. Pumping at high flow rates induces large decreases in particulate As and Fe, a moderate increase in dissolved [As] and As(III)/As ratio, while little change in major ion chemistry. The δD and δ18O are similar for the borehole and fracture waters, suggesting a same source of recharge from atmospheric precipitation. Results support a conceptual model invoking flow and sorption controls on groundwater [As] in fractured bedrock aquifers whereby oxygen infiltration promotes oxidation of As-bearing sulfides at shallower depths in the oxic portion of the flow path releasing As and Fe; followed by Fe oxidation to form Fe oxyhydroxide particulates, which are transported in fractures and sorb As along the flow path until intercepted by boreholes. In the anoxic portions of the flow path, reductive dissolution of As-sorbed iron particulates could re-mobilize As. For exposure assessment, we recommend sampling of groundwater without filtration to obtain total As concentration in groundwater. PMID:24842411

Water-Chemistry and On-Site Sulfur-Speciation Data for Selected Springs in Yellowstone National Park, Wyoming, 1996-1998

USGS Publications Warehouse

Ball, James W.; Nordstrom, D. Kirk; McCleskey, R. Blaine; Schoonen, Martin A.A.; Xu, Yong

2001-01-01

Fifty-eight water analyses are reported for samples collected from 19 hot springs and their overflow drainages and one ambient-temperature acid stream in Yellowstone National Park (YNP) during 1996-98. These water samples were collected and analyzed as part of research investigations on microbially mediated sulfur oxidation in stream waters and sulfur redox speciation in hot springs in YNP and chemical changes in overflow drainages that affect major ions, redox species, and trace elements. The research on sulfur redox speciation in hot springs is a collaboration with the State University of New York at Stony Brook, Northern Arizona University, and the U.S. Geological Survey (USGS). One ambient-temperature acidic stream system, Alluvium Creek and its tributaries in Brimstone Basin, was studied in detail. Analyses were performed adjacent to the sampling site, in an on-site mobile laboratory truck, or later in a USGS laboratory, depending on stability and preservability of the constituent. Water temperature, specific conductance, pH, Eh, dissolved oxygen (D.O.), and dissolved H2S were determined on-site at the time of sampling. Alkalinity and F were determined within a few days of sample collection by titration and by ion-selective electrode, respectively. Concentrations of S2O3 and SxO6 were determined as soon as possible (minutes to hours later) by ion chromatography (IC). Concentrations of Cl, SO4, and Br were determined by IC within a few days of sample collection. Concentrations of Fe(II) and Fe(total) were determined by ultraviolet/visible spectrophotometry within a few days of sample collection. Densities were determined later in the USGS laboratory. Concentrations of Li, Na, and K were determined by flame atomic absorption (Li) and emission (Na, K) spectrometry. Concentrations of Al, As(total), B, Ba, Be, Ca, Cd, Co, Cr, Cu, Fe(total), Mg, Mn, Ni, Pb, Si, Sr, V, and Zn were determined by inductively-coupled plasma optical emission spectrometry. Trace concentrations of Cd, Se, As(total), Ni, and Pb were determined by Zeeman-corrected graphite-furnace atomic-absorption spectrometry. Trace concentrations of As(total) and As(III) were determined by hydride generation using a flow-injection analysis system.

Heavy metals content in acid mine drainage at abandoned and active mining area

NASA Astrophysics Data System (ADS)

Hatar, Hazirah; Rahim, Sahibin Abd; Razi, Wan Mohd; Sahrani, Fathul Karim

2013-11-01

This study was conducted at former Barite Mine, Tasik Chini and former iron mine Sungai Lembing in Pahang, and also active gold mine at Lubuk Mandi, Terengganu. This study was conducted to determine heavy metals content in acid mine drainage (AMD) at the study areas. Fourteen water sampling stations within the study area were chosen for this purpose. In situ water characteristic determinations were carried out for pH, electrical conductivity (EC), redox potential (ORP) and total dissolved solid (TDS) using multi parameter YSI 556. Water samples were collected and analysed in the laboratory for sulfate, total acidity and heavy metals which follow the standard methods of APHA (1999) and HACH (2003). Heavy metals in the water samples were determined directly using Inductive Coupled Plasma Mass Spectrometry (ICP-MS). Data obtained showed a highly acidic mean of pH values with pH ranged from 2.6 ± 0.3 to 3.2 ± 0.2. Mean of electrical conductivity ranged from 0.57 ± 0.25 to 1.01 ± 0.70 mS/cm. Redox potential mean ranged from 487.40 ± 13.68 to 579.9 ± 80.46 mV. Mean of total dissolved solids (TDS) in AMD ranged from 306.50 ± 125.16 to 608.14 ± 411.64 mg/L. Mean of sulfate concentration in AMD ranged from 32.33 ± 1.41 to 207.08 ± 85.06 mg/L, whereas the mean of total acidity ranged from 69.17 ± 5.89 to 205.12 ± 170.83 mgCaCO3/L. Heavy metals content in AMD is dominated by Fe, Cu, Mn and Zn with mean concentrations range from 2.16 ± 1.61 to 36.31 ± 41.02 mg/L, 0.17 ± 0.13 to 11.06 ± 2.85 mg/L, 1.12 ± 0.65 to 7.17 ± 6.05 mg/L and 0.62 ± 0.21 to 6.56 ± 4.11 mg/L, respectively. Mean concentrations of Ni, Co, As, Cd and Pb were less than 0.21, 0.51, 0.24, 0.05 and 0.45 mg/L, respectively. Significant correlation occurred between Fe and Mn, Cu, Zn, Co and Cd. Water pH correlated negatively with all the heavy metals, whereas total acidity, sulfate, total dissolved solid, and redox potential correlated positively. The concentration of heavy metals in the AMD appeared to be influenced by acidity and the formation of Fe, Mn oxide and hydroxide.

Laboratory and field evaluation of a flushable oxic limestone drain for treatment of net-acidic drainage from a flooded anthracite mine, Pennsylvania, USA

USGS Publications Warehouse

Cravotta, C.A.

2008-01-01

This paper demonstrates the use of dissolution-rate data obtained in the laboratory to indicate the potential quality of effluent from a field-scale oxic limestone drain (OLD) treatment system for neutralization of dilute acidic mine drainage (AMD). Effluent from the Reevesdale Mine South Dip Tunnel, a large source of AMD and base flow to the Wabash Creek and Little Schuylkill River in the Southern Anthracite Coalfield of east-central Pennsylvania, is representative of AMD with low concentrations but high loadings of dissolved Fe, Al and other metals because of a high flow rate. In January 2003, rapid neutralization of the AMD from the Reevesdale Mine was achieved in laboratory tests of its reaction rate with crushed limestone in closed, collapsible containers (Cubitainers). The tests showed that net-alkaline effluent could be achieved with retention times greater than 3 h and that effluent alkalinities and associated dissolution rates were equivalent for Fe(OH)3-coated and uncoated limestone. On the basis of the laboratory results, a flushable OLD containing 1450 metric tons of high-purity calcitic limestone followed by two 0.7-m deep wetlands were constructed at the Reevesdale Mine. During the first year of operation, monthly data at the inflow, outflow and intermediate points within the treatment system were collected (April 2006-2007). The inflow to the treatment system ranged from 6.8 to 27.4 L/s, with median pH of 4.7, net acidity of 9.1 mg/L CaCO3, and concentrations of dissolved Al, Fe and Mn of 1.0, 1.9 and 0.89 mg/L, respectively. The corresponding effluent from the OLD had computed void-volume retention times of 4.5-18 h, with median pH of 6.6, net acidity of -93.2 mg/L CaCO3, and concentrations of dissolved Al, Fe and Mn of <0.1, 0.08 and 0.52 mg/L, respectively. The wetlands below the OLD were effective for retaining metal-rich solids flushed at monthly or more frequent intervals from the OLD, but otherwise had little effect on the effluent quality. During the first year of operation, approximately 43 metric tons of limestone were dissolved and 2 metric tons of Al, Fe and Mn were precipitated within the OLD. However, because of the accumulation of these metals within the OLD and possibly other debris from the mine, the effectiveness of the treatment system declined. Despite the installation of a flush-pipe network at the base of the OLD to remove precipitated solids, the limestone bed clogged near the inflow. Consequently, a large fraction of the AMD bypassed the treatment system. To promote flow through the OLD, the flush pipes were open continuously during the last 4 months of the study; however, this effluent was only partially treated because short-circuiting through the pipes decreased contact between the effluent and limestone. A reconfiguration of the flow path through the limestone bed from horizontal to vertical upward could increase the limestone surface area exposed to the metal-laden influent, increase the cross-sectional area perpendicular to flow, decrease the flow path for solids removal, and, consequently, decrease potential for clogging.

A physical catalyst for the electrolysis of nitrogen to ammonia

PubMed Central

Johnson, Daniel; Peng, Rui; Hensley, Dale K.; Bonnesen, Peter V.; Yang, Fengchang; Zhang, Fei; Tschaplinski, Timothy J.; Engle, Nancy L.; Wu, Zili; Meyer, Harry M.; Sumpter, Bobby G.

2018-01-01

Ammonia synthesis consumes 3 to 5% of the world’s natural gas, making it a significant contributor to greenhouse gas emissions. Strategies for synthesizing ammonia that are not dependent on the energy-intensive and methane-based Haber-Bosch process are critically important for reducing global energy consumption and minimizing climate change. Motivated by a need to investigate novel nitrogen fixation mechanisms, we herein describe a highly textured physical catalyst, composed of N-doped carbon nanospikes, that electrochemically reduces dissolved N2 gas to ammonia in an aqueous electrolyte under ambient conditions. The Faradaic efficiency (FE) achieves 11.56 ± 0.85% at −1.19 V versus the reversible hydrogen electrode, and the maximum production rate is 97.18 ± 7.13 μg hour−1 cm−2. The catalyst contains no noble or rare metals but rather has a surface composed of sharp spikes, which concentrates the electric field at the tips, thereby promoting the electroreduction of dissolved N2 molecules near the electrode. The choice of electrolyte is also critically important because the reaction rate is dependent on the counterion type, suggesting a role in enhancing the electric field at the sharp spikes and increasing N2 concentration within the Stern layer. The energy efficiency of the reaction is estimated to be 5.25% at the current FE of 11.56%. PMID:29719860

Effects of an Asian Dust Storm on the Gulf of Alaska: Trace Metal Evidence and Biological Consequences

NASA Astrophysics Data System (ADS)

Crispo, S. M.; Peterson, T. D.; Lohan, M. C.; Crawford, D.; Orians, K. J.; Harrison, P. J.; Statham, P. J.

2004-12-01

In April 2001, a large dust storm originating in the Gobi and Takla Makan deserts resulted in large quantities of dust to be transported to the northeastern Pacific Ocean. Off the California coast, dissolved iron and aluminum concentrations determined before and after the dust traversed the North Pacific show increases of 0.5nM and 2nM respectively (Johnson, 2003). The most concentrated plume of dust traveled toward the eastern Gulf of Alaska. Every year anticyclonic mesoscale eddies, transporting coastal waters offshore, form off the coast of the Queen Charlotte Islands, British Columbia. These Haida eddies begin with high concentrations of trace metals which deplete over time. Evidence of 2001-dust deposition is seen in elevated dissolved aluminum concentrations (up to 7nM) in the eddy, which stay elevated months after the dust was deposited. By June 2001, dissolved zinc concentrations in the eddy surface mixed layer are low (below 0.3nM) and decrease slightly by September 2001. Dissolved cadmium concentrations dropped drastically (from 0.4nM to 0.09nM) from June to September 2001 in the Haida-2001 eddy coinciding with a large increase in coccolithophore production. This coccolithophore increase was five times greater than what was seen in the Haida-2000 eddy and twenty times that of the reference station. Based on our observations and by comparison with a shipboard Zn-Fe-enrichment study, we hypothesize that dust deposition into surface waters promotes growth first of diatoms and then of coccolithophores once zinc is depleted. The presence of dust remnants held within a quasi-isolated mesoscale eddy allows us to draw conclusions about succession following dust deposition events and yields further information regarding interactions between trace metal supply and primary production in the NE Subarctic Pacific.

Zn0-CNTs-Fe3O4 catalytic in situ generation of H2O2 for heterogeneous Fenton degradation of 4-chlorophenol.

PubMed

Yang, Zhao; Gong, Xiao-Bo; Peng, Lin; Yang, Dan; Liu, Yong

2018-06-04

A novel Zn 0 -CNTs-Fe 3 O 4 composite was synthesized by the chemical co-precipitation combined with high sintering process at nitrogen atmosphere. The as-prepared composite was characterized by SEM, EDS, XRD, XPS, VSM and N 2 adsorption/desorption experiments. A novel heterogeneous Fenton-like system, composed of Zn 0 -CNTs-Fe 3 O 4 composite and dissolved oxygen (O 2 ) in solution, which can in situ generate H 2 O 2 and OH, was used for the degradation of 4-chlorophenol (4-CP). The influences of various operational parameters, including the initial pH, dosage of Zn 0 -CNTs-Fe 3 O 4 and initial concentration of 4-CP on the removal of 4-CP were investigated. The removal efficiencies of 4-CP and total organic carbon (TOC) were 99% and 57%, respectively, at the initial pH of 1.5, Zn 0 -CNTs-Fe 3 O 4 dosage of 2 g/L, 4-CP initial concentration of 50 mg/L and oxygen flow rate of 400 mL/min. Based on the results of the radical scavenger effect study, the hydroxyl radical was considered as the main reactive oxidants in Zn 0 -CNTs-Fe 3 O 4 /O 2 system and a possible degradation pathway of 4-CP was proposed. Copyright © 2018. Published by Elsevier Ltd.

Reactive transport modeling of geochemical controls on secondary water quality impacts at a crude oil spill site near Bemidji, MN

USGS Publications Warehouse

Ng, Gene-Hua Crystal.; Bekins, Barbara A.; Cozzarelli, Isabelle M.; Baedecker, Mary Jo; Bennett, Philip C.; Amos, Richard T.; Herkelrath, William N.

2015-01-01

Anaerobic biodegradation of organic amendments and contaminants in aquifers can trigger secondary water quality impacts that impair groundwater resources. Reactive transport models help elucidate how diverse geochemical reactions control the spatiotemporal evolution of these impacts. Using extensive monitoring data from a crude oil spill site near Bemidji, Minnesota (USA), we implemented a comprehensive model that simulates secondary plumes of depleted dissolved O2 and elevated concentrations of Mn2+, Fe2+, CH4, and Ca2+ over a two-dimensional cross section for 30 years following the spill. The model produces observed changes by representing multiple oil constituents and coupled carbonate and hydroxide chemistry. The model includes reactions with carbonates and Fe and Mn mineral phases, outgassing of CH4 and CO2 gas phases, and sorption of Fe, Mn, and H+. Model results demonstrate that most of the carbon loss from the oil (70%) occurs through direct outgassing from the oil source zone, greatly limiting the amount of CH4 cycled down-gradient. The vast majority of reduced Fe is strongly attenuated on sediments, with most (91%) in the sorbed form in the model. Ferrous carbonates constitute a small fraction of the reduced Fe in simulations, but may be important for furthering the reduction of ferric oxides. The combined effect of concomitant redox reactions, sorption, and dissolved CO2 inputs from source-zone degradation successfully reproduced observed pH. The model demonstrates that secondary water quality impacts may depend strongly on organic carbon properties, and impacts may decrease due to sorption and direct outgassing from the source zone.

Atmospheric hydrogen peroxide and Eoarchean iron formations.

PubMed

Pecoits, E; Smith, M L; Catling, D C; Philippot, P; Kappler, A; Konhauser, K O

2015-01-01

It is widely accepted that photosynthetic bacteria played a crucial role in Fe(II) oxidation and the precipitation of iron formations (IF) during the Late Archean-Early Paleoproterozoic (2.7-2.4 Ga). It is less clear whether microbes similarly caused the deposition of the oldest IF at ca. 3.8 Ga, which would imply photosynthesis having already evolved by that time. Abiological alternatives, such as the direct oxidation of dissolved Fe(II) by ultraviolet radiation may have occurred, but its importance has been discounted in environments where the injection of high concentrations of dissolved iron directly into the photic zone led to chemical precipitation reactions that overwhelmed photooxidation rates. However, an outstanding possibility remains with respect to photochemical reactions occurring in the atmosphere that might generate hydrogen peroxide (H2 O2 ), a recognized strong oxidant for ferrous iron. Here, we modeled the amount of H2 O2 that could be produced in an Eoarchean atmosphere using updated solar fluxes and plausible CO2 , O2 , and CH4 mixing ratios. Irrespective of the atmospheric simulations, the upper limit of H2 O2 rainout was calculated to be <10(6) molecules cm(-2) s(-1) . Using conservative Fe(III) sedimentation rates predicted for submarine hydrothermal settings in the Eoarchean, we demonstrate that the flux of H2 O2 was insufficient by several orders of magnitude to account for IF deposition (requiring ~10(11) H2 O2 molecules cm(-2) s(-1) ). This finding further constrains the plausible Fe(II) oxidation mechanisms in Eoarchean seawater, leaving, in our opinion, anoxygenic phototrophic Fe(II)-oxidizing micro-organisms the most likely mechanism responsible for Earth's oldest IF. © 2014 John Wiley & Sons Ltd.

When soils become sediments: Large-scale storage of soils in sandpits and lakes and the impact of reduction kinetics on heavy metals and arsenic release to groundwater.

PubMed

Vink, Jos P M; van Zomeren, Andre; Dijkstra, Joris J; Comans, Rob N J

2017-08-01

Simulating the storage of aerobic soils under water, the chemical speciation of heavy metals and arsenic was studied over a long-term reduction period. Time-dynamic and redox-discrete measurements in reactors were used to study geochemical changes. Large kinetic differences in the net-complexation quantities of heavy metals with sulfides was observed, and elevated pore water concentrations remained for a prolonged period (>1 year) specifically for As, B, Ba, Co, Mo, and Ni. Arsenic is associated to the iron phases as a co-precipitate or sorbed fraction to Fe-(hydr)oxides, and it is being released into solution as a consequence of the reduction of iron. The composition of dissolved organic matter (DOM) in reducing pore water was monitored, and relative contributions of fulvic, humic and hydrophylic compounds were measured via analytical batch procedures. Quantitative and qualitative shifts in organic compounds occur during reduction; DOM increased up to a factor 10, while fulvic acids become dominant over humic acids which disappear altogether as reduction progresses. Both the hydrophobic and hydrophilic fractions increase and may even become the dominant fraction. Reactive amorphous and crystalline iron phases, as well as dissolved FeII/FeIII speciation, were measured and used as input for the geochemical model to improve predictions for risk assessment to suboxic and anaerobic environments. The release of arsenic is related to readily reducible iron fractions that may be identified by 1 mM CaCl 2 extraction procedure. Including DOM concentration shifts and compositional changes during reduction significantly improved model simulations, enabling the prediction of peak concentrations and identification of soils with increased emission risk. Practical methods are suggested to facilitate the practice of environmentally acceptable soil storage under water. Copyright © 2017 Elsevier Ltd. All rights reserved.

The unique self-assembly/disassembly property of Archaeoglobus fulgidus ferritin and its implications on molecular release from the protein cage.

PubMed

Sana, Barindra; Johnson, Eric; Lim, Sierin

2015-12-01

In conventional in vitro encapsulation of molecular cargo, the multi-subunit ferritin protein cages are disassembled in extremely acidic pH and re-assembled in the presence of highly concentrated cargo materials, which results in poor yields due to the low-pH treatment. In contrast, Archaeoglobus fulgidus open-pore ferritin (AfFtn) and its closed-pore mutant (AfFtn-AA) are present as dimeric species in neutral buffers that self-assemble into cage-like structure upon addition of metal ions. To understand the iron-mediated self-assembly and ascorbate-mediated disassembly properties, we studied the iron binding and release profile of the AfFtn and AfFtn-AA, and the corresponding oligomerization of their subunits. Fe(2+) binding and conversion to Fe(3+) triggered the self-assembly of cage-like structures from dimeric species of AfFtn and AfFtn-AA subunits, while disassembly was induced by dissolving the iron core with reducing agents. The closed-pore AfFtn-AA has identical iron binding kinetics but lower iron release rates when compared to AfFtn. While the iron binding rate is proportional to Fe(2+) concentration, the iron release rate can be controlled by varying ascorbate concentrations. The AfFtn and AfFtn-AA cages formed by iron mineralization could be disassembled by dissolving the iron core. The open-pores of AfFtn contribute to enhanced reductive iron release while the small channels located at the 3-fold symmetry axis (3-fold channels) are used for iron uptake. The iron-mediated self-assembly/disassembly property of AfFtn offers a new set of molecular trigger for formation and dissociation of the protein cage, which can potentially regulate uptake and release of molecular cargo from protein cages. Copyright © 2015 Elsevier B.V. All rights reserved.

Trace metal dynamics in zooplankton from the Bay of Bengal during summer monsoon.

PubMed

Rejomon, G; Kumar, P K Dinesh; Nair, M; Muraleedharan, K R

2010-12-01

Trace metal (Fe, Co, Ni, Cu, Zn, Cd, and Pb) concentrations in zooplankton from the mixed layer were investigated at 8 coastal and 20 offshore stations in the western Bay of Bengal during the summer monsoon of 2003. The ecotoxicological importance of trace metal uptake was apparent within the Bay of Bengal zooplankton. There was a distinct spatial heterogeneity of metals, with highest concentrations in the upwelling zones of the southeast coast, moderate concentrations in the cyclonic eddy of the northeast coast, and lowest concentrations in the open ocean warm gyre regions. The average trace metal concentrations (μg g⁻¹) in coastal zooplankton (Fe, 44894.1 ± 12198.2; Co, 46.2 ± 4.6; Ni, 62.8 ± 6.5; Cu, 84.9 ± 6.7; Zn, 7546.8 ± 1051.7; Cd, 46.2 ± 5.6; Pb, 19.2 ± 2.6) were higher than in offshore zooplankton (Fe, 3423.4 ± 681.6; Co, 19.5 ± 3.81; Ni, 25.3 ± 7.3; Cu, 29.4 ± 4.2; Zn, 502.3 ± 124.3; Cd, 14.3 ± 2.9; Pb, 3.2 ± 2.0). A comparison of average trace metal concentrations in zooplankton from the Bay of Bengal showed enrichment of Fe, Co, Ni, Cu, Zn, Cd, and Pb in coastal zooplankton may be related to metal absorption from primary producers, and differences in metal concentrations in phytoplankton from coastal waters (upwelling zone and cyclonic eddy) compared with offshore waters (warm gyre). Zooplankton showed a great capacity for accumulations of trace metals, with average concentration factors of 4 867 929 ± 569 971, 246 757 ± 51 321, 337 180 ± 125 725, 43 480 ± 11 212, 1 046 371 ± 110 286, 601 679 ± 213 949, and 15 420 ± 9201 for Fe, Co, Ni, Cu, Zn, Cd, and Pb with respect to dissolved concentrations in coastal and offshore waters of the Bay of Bengal. © 2009 Wiley Periodicals, Inc. Environ Toxicol, 2009. Copyright © 2009 Wiley Periodicals, Inc.

Response of the unicellular diazotrophic cyanobacterium Crocosphaera watsonii to iron limitation.

PubMed

Jacq, Violaine; Ridame, Céline; L'Helguen, Stéphane; Kaczmar, Fanny; Saliot, Alain

2014-01-01

Iron (Fe) is widely suspected as a key controlling factor of N2 fixation due to the high Fe content of nitrogenase and photosynthetic enzymes complex, and to its low concentrations in oceanic surface seawaters. The influence of Fe limitation on the recently discovered unicellular diazotrophic cyanobacteria (UCYN) is poorly understood despite their biogeochemical importance in the carbon and nitrogen cycles. To address this knowledge gap, we conducted culture experiments on Crocosphaera watsonii WH8501 growing under a range of dissolved Fe concentrations (from 3.3 to 403 nM). Overall, severe Fe limitation led to significant decreases in growth rate (2.6-fold), C, N and chlorophyll a contents per cell (up to 4.1-fold), N2 and CO2 fixation rates per cell (17- and 7-fold) as well as biovolume (2.2-fold). We highlighted a two phased response depending on the degree of limitation: (i) under a moderate Fe limitation, the biovolume of C. watsonii was strongly reduced, allowing the cells to keep sufficient energy to maintain an optimal growth, volume-normalized contents and N2 and CO2 fixation rates; (ii) with increasing Fe deprivation, biovolume remained unchanged but the entire cell metabolism was affected, as shown by a strong decrease in the growth rate, volume-normalized contents and N2 and CO2 fixation rates. The half-saturation constant for growth of C. watsonii with respect to Fe is twice as low as that of the filamentous Trichodesmium indicating a better adaptation of C. watsonii to poor Fe environments than filamentous diazotrophs. The physiological response of C. watsonii to Fe limitation was different from that previously shown on the UCYN Cyanothece sp, suggesting potential differences in Fe requirements and/or Fe acquisition within the UCYN community. These results contribute to a better understanding of how Fe bioavailability can control the activity of UCYN and explain the biogeography of diverse N2 fixers in ocean.

Elucidating the Role of Carbon Sources on Abiotic and Biotic Release of Arsenic into Cambodian Aquifers

NASA Astrophysics Data System (ADS)

Koeneke, M.

2017-12-01

Arsenic (As) is a naturally occurring contaminant in Cambodia that has been contaminating well-water sources of millions of people. Commonly, studies look into the biotic factors that cause the arsenic to be released from aquifer sediments to groundwater. However, abiotic release of As from sediments, though little studied, may also play key roles in As contamination of well water. The goal of this research is to quantitatively compare organic-carbon mediated abiotic and biotic release of arsenic from sediments to groundwater. Batch anaerobic incubation experiments under abiotic (sodium azide used to immobilize microbes) and biotic conditions were conducted using Cambodian aquifer sediments, four different organic carbon sources (sodium lactate, sodium citrate, sodium oxalate, and humic acid), and six different carbon concentrations (0, 1, 2.5, 5, 10, 25mg C/L). Dissolved arsenic, iron(Fe), and manganese(Mn) concentrations in the treatments were measured 112 days . In addition, sediment and solution carbon solution was measured . Collectively, these show how different carbon sources, different carbon concentrations, and how abiotic and biotic factors impact the release of arsenic from Cambodian sediments into aquifers. Overall, an introduction of organic carbon to the soil increases the amount of As released from the sediment. The biotic + abiotic and abiotic conditions seemed to play a minimal role in the amount of As released. Dissolved species analysis showed us that 100% of the As was As(V), Our ICP-MS results vary due to the heterogeneity of samples, but when high levels are Fe are seen in solution, we also see high levels of As. We also see higher As concentrations when there is a smaller amount of Mn in solution.

Manganese and iron as oxygen carriers to anoxie estuarine sediment

NASA Astrophysics Data System (ADS)

Brayner, F. M. M.; Matvienko, B.

2003-05-01

We studied the concentration of a series of transition metals including Mn and Fe in an estuarine fishpond. The pond is situated at latitude 8°10'S and longitude 34°55'W, in the Capibaribe River estuary, within the Recife city boundaries, which is located in Pernambuco, a state of the Brazilian Northeast Pond area is 1.5 ha and it bas a 0.5 m depth. It is separated from the river by dikes. Water temperature at 28° C is stable throughout the year. Light breezes keep the water aerated, but intense ongoing decomposition makes the sediment anoxie. The area, originally of mangrove type, has been changed by antropic action on its fauna and vegetation. The study focuses on changes in behaviour of heavy metals. Samples of bottom sediments wore collected by Eckman dredge sediment sampler and total metal concentration was determined by the lithium borate fusion method. Water, recent sediment, and consolidated sediment were examined in this fishpond where Mn and Fe are brought in periodically by water and then gradually go into the sediment at respective rates of 10.52 and 1332 mg m^{-2}a^{-1}. Strong bioturbation re-suspends sediment while simultaneously re-dissolution of these ions is going on fhrough reduction in the anoxie sédiment. As soluble species these ions migrate from sediment to water and are there continually oxidized by dissolved oxygen, becoming insoluble. With their precipitation, chemically bound oxygen is carried down to the sediment, constituting a parallel channel of transport in addition to migration into the sediment bydiffusion of the oxygen dissolved in the water. The estimated flow rates are 3.25 and 76 mg O2 m^{-2}a^{-1} due to Mn and Fe respectively. The rates were established using natural silicon as a tracer.

Interactions between iron and organic matter may influence the fate of permafrost carbon in the Arctic

NASA Astrophysics Data System (ADS)

Cory, R. M.; Trusiak, A.; Ward, C.; Kling, G. W.; Tfaily, M.; Paša-Tolić, L.; Noel, V.; Bargar, J.

2017-12-01

The ongoing thawing of permafrost soils is the only environmental change that allows tremendous stores of organic carbon (C) to be converted into carbon dioxide (CO2) on decadal time scales, thus providing a positive and accelerating feedback to global warming. Evidence suggests that iron enhances abiotic reactions that convert dissolved organic matter (DOM) to CO2 in dark soils and in sunlit surface waters depending on its redox state and association with DOM (i.e., iron-DOM complexation). However, the complexation of iron in surface waters and soils remains too poorly understood to predict how iron influences the rates of oxidation of DOM to CO2. To address this knowledge gap, we characterized iron-DOM complexation in iron-rich soil and surface waters of the Arctic, in combination with measurements of DOM oxidation to CO2. These waters contain high concentrations of dissolved iron and DOM (up to 1 and 2 mM, respectively), and low concentrations of other potential ligands for iron such as sulfide, carbonate, chloride, or bromide. Ultra-high resolution mass spectrometry (FT-ICR MS) was used to identify ligands for iron within the DOM pool, and synchrotron based X-ray analysis (XAS and EXAFS) was used to assess iron's oxidation state, to detect iron complexation, and to constrain the chemical composition of the complexes. Across a natural gradient of dissolved iron and DOM concentrations, many potential ligands were identified within DOM that are expected to complex with iron (e.g., aromatic acids). EXAFS showed substantial complexation of reduced ferrous iron (Fe(II)) to DOM in arctic soil waters, on the basis of comparison to Fe(II)-DOM reference spectra. Identification of iron complexed to DOM in soil waters is consistent with strongly co-varying iron and DOM concentrations in arctic soil and surface waters, and supports our hypothesis that complexation of iron by DOM influences dark and light redox reactions that oxidize DOM to CO2. Understanding the molecular controls on the biogeochemical reactions that convert permafrost carbon to CO2 is critical for understanding the role of the Arctic in current and future climate change.

Geochemistry of dissolved inorganic carbon in a Coastal Plain aquifer. 1. Sulfate from confining beds as an oxidant in microbial CO2 production

USGS Publications Warehouse

Chapelle, F.H.; McMahon, P.B.

1991-01-01

A primary source of dissolved inorganic carbon (DIC) in the Black Creek aquifer of South Carolina is carbon dioxide produced by microbially mediated oxidation of sedimentary organic matter. Groundwater chemistry data indicate, however, that the available mass of inorganic electron acceptors (oxygen, Fe(III), and sulfate) and observed methane production is inadequate to account for observed CO2 production. Although sulfate concentrations are low (approximately 0.05-0.10 mM) in aquifer water throughout the flow system, sulfate concentrations are greater in confining-bed pore water (0.4-20 mM). The distribution of culturable sulfate-reducing bacteria in these sediments suggests that this concentration gradient is maintained by greater sulfate-reducing activity in sands than in clays. Calculations based on Fick's Law indicate that possible rates of sulfate diffusion to aquifer sediments are sufficient to explain observed rates of CO2 production (about 10-5 mmoll-1 year-1), thus eliminating the apparent electron-acceptor deficit. Furthermore, concentrations of dissolved hydrogen in aquifer water are in the range characteristic of sulfate reduction (2-6 nM), which provides independent evidence that sulfate reduction is the predominant terminal electron-accepting process in this system. The observed accumulation of pyrite- and calcite-cemented sandstones at sand-clay interfaces is direct physical evidence that these processes have been continuing over the history of these sediments. ?? 1991.

Critical evaluation of the stability of highly concentrated LiTFSI - Acetonitrile electrolytes vs. graphite, lithium metal and LiFePO4 electrodes

NASA Astrophysics Data System (ADS)

Nilsson, Viktor; Younesi, Reza; Brandell, Daniel; Edström, Kristina; Johansson, Patrik

2018-04-01

Highly concentrated LiTFSI - acetonitrile electrolytes have recently been shown to stabilize graphite electrodes in lithium-ion batteries (LIBs) much better than comparable more dilute systems. Here we revisit this system in order to optimise the salt concentration vs. both graphite and lithium metal electrodes with respect to electrochemical stability. However, we observe an instability regardless of concentration, making lithium metal unsuitable as a counter electrode, and this also affects evaluation of e.g. graphite electrodes. While the highly concentrated electrolytes have much improved electrochemical stabilities, their reductive decomposition below ca. 1.2 V vs. Li+/Li° still makes them less practical vs. graphite electrodes, and the oxidative reaction with Al at ca. 4.1 V vs. Li+/Li° makes them problematic for high voltage LIB cells. The former originates in an insufficiently stable solid electrolyte interphase (SEI) dissolving and continuously reforming - causing self-discharge, as observed by paused galvanostatic cycling, while the latter is likely caused by aluminium current collector corrosion. Yet, we show that medium voltage LiFePO4 positive electrodes can successfully be used as counter and reference electrodes.

Chemical dynamics of acidity and heavy metals in a mine water-polluted soil during decontamination using clean water.

PubMed

Chen, A; Lin, C; Lu, W; Ma, Y; Bai, Y; Chen, H; Li, J

2010-03-15

A column leaching experiment was conducted to investigate the chemical dynamics of the percolating water and washed soil during decontamination of an acidic mine water-polluted soil. The results show that leaching of the contaminated soil with clean water rapidly reduced soluble acidity and ion concentrations in the soils. However, only <20% of the total actual acidity in the soil column was eliminated after 30 leaching cycles. It is likely that the stored acidity continues to be released to the percolating water over a long period of time. During the column leaching, dissolved Cu and Pb were rapidly leached out, followed by mobilization of colloidal Cu and Pb from the exchangeable and the oxide-bound fractions as a result of reduced ionic strength in the soil solution. The soluble Fe contained in the soil was rare, probably because the soil pH was not sufficiently low; marked mobility of colloidal Fe took place after the ionic strength of the percolating water was weakened and the mobilized Fe was mainly derived from iron oxides. In contrast with Cu, Pb and Fe, the concentration of leachate Zn and Mn showed a continuously decreasing trend during the entire period of the experiment. (c) 2009 Elsevier B.V. All rights reserved.

Adsorption and Pore of Physical-Chemical Activated Coconut Shell Charcoal Carbon

NASA Astrophysics Data System (ADS)

Budi, E.; Umiatin, U.; Nasbey, H.; Bintoro, R. A.; Wulandari, Fi; Erlina, E.

2018-04-01

The adsorption of activated carbon of coconut shell charcoal on heavy metals (Cu and Fe) of the wastewater and its relation with the carbon pore structure was investigated. The coconut shell was pyrolized in kiln at temperature about 75 - 150 °C for about 6 hours to produce charcoal and then shieved into milimeter sized granule particles. Chemical activation was done by immersing the charcoal into chemical solution of KOH, NaOH, HCl and H3PO4, with various concentration. The activation was followed by physical activation using horizontal furnace at 400°C for 1 hours in argon gas environment with flow rate of 200 kg/m3. The surface morphology of activated carbon were characterized by using Scanning Electron Microscopy (SEM). Wastewater was made by dissolving CuSO4.5H2O and FeSO4.7H2O into aquades. The metal adsorption was analized by using Atomic Absorption Spectroscopy (AAS). The result shows that in general, the increase of chemical concentration cause the increase of pore number of activated carbon due to an excessive chemical attack and lead the increase of adsorption. However it tend to decrease as further increasing in chemical activator concentration due to carbon collapsing. In general, the adsorption of Cu and Fe metal from wastewater by activated carbon increased as the activator concentration was increased.

[Dynamics of upland field P pool under a long-term application of fertilizer P in yellow soil area and their effects on P concentration in runoff].

PubMed

Liu, Fang; Huang, Changyong; He, Tengbin; Qian, Xiaogang; Liu, Yuansheng; Luo, Haibo

2003-02-01

Studies on the dynamics of upland field P pool under a long-term application of fertilizer P in yellow soil area and their effects on P concentration in runoff showed that the contents of A1-P, Fe-P and Ca-P in soil cultivated layer increased greatly, and Olsen-P and algae-available P also accumulated obviously. The correlation coefficients of algae-available P content in the high-P soils (Olsen-P > 25 mg.kg-1) with the quantities of A1-P, Fe-P and Ca-P were 0.859**, 0.903** and 0.650*, respectively, of which, Fe-P was the most important. By a 30-min rainfall simulation experiment with a constant rainfall rate of 63.2 mm.h-1, the concentrations of dissolved reactive P and bio-available P in runoff from low-P upland fields (Olsen-P 4.62-15.9 mg.kg-1) were 2.81-4.17 micrograms.L-1 and 0.723-0.876 mg.L-1, respectively, whereas their concentrations in runoff from high-P upland fields (Olsen-P 29.4-59.2 mg.kg-1) were 0.026-0.714 mg.L-1 and 0.996-1.281 mg.L-1, respectively. Therefore, runoff from high-P upland fields could accelerate water eutrophication.

Arsenic, metals, and nutrients in runoff from two detention basins to Raccoon Creek, New Jersey Coastal Plain, 2008

USGS Publications Warehouse

Barringer, Julia L.; Szabo, Zoltan; Bonin, Jennifer L.; McGee, Craig K.

2011-01-01

Arsenic (As) concentrations in the waters of Raccoon Creek in southern New Jersey commonly exceed the State\\'s Surface Water Quality Standard (SWQS) for freshwater of 0.017 microgram per liter (mu or ug/L). In order to assess contributions of As from residential runoff to the creek, samples of runoff water were collected from a detention basin in each of two residential developments underlain by different geologic formations and at the outlets of those basins. Samples of streamwater also were collected from Raccoon Creek adjacent to the developments. The samples were analyzed to determine concentrations of As, selected metals, organic carbon, and nutrients. Soil samples in and downgradient from the basins also were collected and analyzed. Concentrations of As in unfiltered water samples of runoff from the basin underlain by glauconitic clays generally were higher (up to 4.35 mu or ug/L) than in runoff from the basin underlain by predominantly quartz sands and silts (up to 2.68 mu or ug/L). Chromium (Cr) concentrations also were higher in runoff from the basin underlain by glauconitic clays than in runoff from the basin underlain by quartz sand and silt. In addition, Cr concentrations were higher in the glauconitic soils than in the quartz-rich soils. Metals such as aluminum (Al), iron (Fe), lead (Pb), and manganese (Mn) in the runoff and in the streamwater were mostly in particulate form. Arsenic, most metals, and phosphorus (P) however, were mostly in dissolved form in runoff but in particulate form in the streamwater. Total organic carbon concentrations in the runoff ranged from about 10 to nearly 16 milligrams per liter (mg/L). Given such levels of organic carbon and strong correlations between concentrations of some metals and organic carbon, it may be that many of the metals were complexed with dissolved organic carbon and transported in that form in the runoff. Although underlying geologic materials and soils appear to be major contributors of As to the streamwater, As also could have been contributed from lead arsenate pesticide residues. The residential development underlain by quartz-rich sediments formerly had been an orchard where such pesticides may have been used. The substantial inputs of As to runoff at this site may be attributable to this former land use, although Pb concentrations were about the same in runoff from both sites. The streamwater at both sites, however, contained Pb concentrations well above those in runoff, indicating that there are additional inputs of Pb, perhaps from roadside soils, upstream from the two sampling sites in this study. Positive relations between concentrations of As and some metals with dissolved organic carbon in runoff and streamwater indicate that complexation with organic carbon may provide a mechanism by which these constituents can be transported. Sorption of As, Pb, and P to Fe hydroxides may be indicated by the observed positive relation of particulate As, Pb, and P to particulate Fe, however, representing an additional mechanism for transport of these constituents.

Arsenic mobilization in the Brahmaputra plains of Assam: groundwater and sedimentary controls.

PubMed

Sailo, Lalsangzela; Mahanta, Chandan

2014-10-01

Arsenic (As) mobilization to the groundwater of Brahmaputra floodplains was investigated in Titabor, Jorhat District, located in the North Eastern part of India. The groundwater and the aquifer geochemistry were characterized in the study area. The range of As concentration in the groundwater varies from 10 to 440 μg/l with mean concentration 210 μg/l. The groundwaters are characterized by high dissolved Fe, Mn, and HCO₃(-) and low concentrations of NO₃(-) and SO₄(2-) indicating the reduced conditions prevailing in the groundwater. In order to understand the actual mobilization processes in the area, six core drilling surrounding the two target tube wells (T1 and T2) with high As concentration (three drill-cores surrounds each tube well closely) was done. The sediment was analyzed its chemical, mineralogical, and elemental compositions. A selective sequential extraction suggested that most of the As in the sediment is bound to Fe oxides fractions (32 to 50%) and the competition for adsorption site by anions (PO₄(3-)) also accounts to significant fractions of the total arsenic extracted. High variability in the extraction as well as properties of the sediment was observed due to the heterogeneity of the sediment samples with different chemical properties. The SEM and EDX results indicate the presence of Fe, Mn coating along with As for most of the sample, and the presence of As associated minerals were calculated using PHREEQC. The mobilization of As into the groundwater was anticipated to be largely controlled by the reductive dissolution of Fe oxides and partly by the competitive anions viz. PO₄(3-).

Iron cycling at corroding carbon steel surfaces.

PubMed

Lee, Jason S; McBeth, Joyce M; Ray, Richard I; Little, Brenda J; Emerson, David

2013-01-01

Surfaces of carbon steel (CS) exposed to mixed cultures of iron-oxidizing bacteria (FeOB) and dissimilatory iron-reducing bacteria (FeRB) in seawater media under aerobic conditions were rougher than surfaces of CS exposed to pure cultures of either type of microorganism. The roughened surface, demonstrated by profilometry, is an indication of loss of metal from the surface. In the presence of CS, aerobically grown FeOB produced tight, twisted helical stalks encrusted with iron oxides. When CS was exposed anaerobically in the presence of FeRB, some surface oxides were removed. However, when the same FeOB and FeRB were grown together in an aerobic medium, FeOB stalks were less encrusted with iron oxides and appeared less tightly coiled. These observations suggest that iron oxides on the stalks were reduced and solubilized by the FeRB. Roughened surfaces of CS and denuded stalks were replicated with culture combinations of different species of FeOB and FeRB under three experimental conditions. Measurements of electrochemical polarization resistance established different rates of corrosion of CS in aerobic and anaerobic media, but could not differentiate rate differences between sterile controls and inoculated exposures for a given bulk concentration of dissolved oxygen. Similarly, total iron in the electrolyte could not be used to differentiate treatments. The experiments demonstrate the potential for iron cycling (oxidation and reduction) on corroding CS in aerobic seawater media.

Iron cycling at corroding carbon steel surfaces

PubMed Central

Lee, Jason S.; McBeth, Joyce M.; Ray, Richard I.; Little, Brenda J.; Emerson, David

2013-01-01

Surfaces of carbon steel (CS) exposed to mixed cultures of iron-oxidizing bacteria (FeOB) and dissimilatory iron-reducing bacteria (FeRB) in seawater media under aerobic conditions were rougher than surfaces of CS exposed to pure cultures of either type of microorganism. The roughened surface, demonstrated by profilometry, is an indication of loss of metal from the surface. In the presence of CS, aerobically grown FeOB produced tight, twisted helical stalks encrusted with iron oxides. When CS was exposed anaerobically in the presence of FeRB, some surface oxides were removed. However, when the same FeOB and FeRB were grown together in an aerobic medium, FeOB stalks were less encrusted with iron oxides and appeared less tightly coiled. These observations suggest that iron oxides on the stalks were reduced and solubilized by the FeRB. Roughened surfaces of CS and denuded stalks were replicated with three culture combinations of different species of FeOB and FeRB under three experimental conditions. Measurements of electrochemical polarization resistance established different rates of corrosion of CS in aerobic and anaerobic media, but could not differentiate rate differences between sterile controls and inoculated exposures for a given bulk concentration of dissolved oxygen. Similarly, total iron in the electrolyte could not be used to differentiate treatments. The experiments demonstrate the potential for iron cycling (oxidation and reduction) on corroding CS in aerobic seawater media. PMID:24093730

Atmospheric wet deposition of dissolved trace elements to Jiaozhou Bay, North China: Fluxes, sources and potential effects on aquatic environments.

PubMed

Xing, Jianwei; Song, Jinming; Yuan, Huamao; Wang, Qidong; Li, Xuegang; Li, Ning; Duan, Liqin; Qu, Baoxiao

2017-05-01

To analyze the fluxes, seasonal variations, sources and potential ecological effects of dissolved trace elements (TEs) in atmospheric wet deposition (AWD), one-year wet precipitation samples were collected and determined for nine TEs in Jiaozhou Bay (JZB) between June 2015 and May 2016. Both the volume-weighted mean (VWM) concentration and flux sequence for the measured TEs was Al > Mn > Zn > Fe > Pb > Se > Cr > Cd > Co. Al was the most abundant TE with a VWM concentration and wet flux of 33.8 μg L -1 and 29.2 mg m -2  yr -1 , which were 2 and 3 orders of magnitude higher than those of Co, respectively. The emission intensities of pollutants, rainfall amount and wind speed were the dominating factors influencing seasonal variations of TEs in AWD. Based on enrichment factors, correlation analysis and principal component analysis, most of the TEs in AWD were primarily originated from anthropogenic activities except for Al and Fe, which are typically derived from re-suspended soil dusts. Although the TE inputs by AWD were significantly lower than those by rivers, the TE inputs via short-term heavy rains would distinctly increase surface seawater TE concentrations and then pollute the marine environment of JZB. AWD would have both profound impacts on the biogeochemical cycles of TEs and dual ecological effects (nutrient and toxicity) on aquatic organisms. Copyright © 2017 Elsevier Ltd. All rights reserved.

Hydrogeologic setting and potential for denitrification in ground water, coastal plain of southern Maryland

USGS Publications Warehouse

Krantz, David E.; Powars, David S.

2000-01-01

The types and distribution of Coastal Plain sediments in the Patuxent River Basin may contribute to relatively low concentrations of nitrate (typically less than 1 milligram per liter) in stream base flow because of the chemical reduction of dissolved nitrate (denitrification) in ground water. Water chemistry data from synoptic stream base-flow surveys in the Patuxent River Basin show higher dissolved nitrate concentrations in the Piedmont than in the Coastal Plain section of the watershed. Stream base flow reflects closely the chemistry of ground water discharging from the surficial (unconfined) aquifer to the stream. Because land use in the sampled subbasins is virtually the same in each section, differences in the physical and geochemical characteristics of the surficial aquifer may explain the observed differences in water chemistry. One possible cause of lower nitrate concentrations in the Coastal Plain is denitrification within marine sediments that contain chemically reduced compounds. During denitrification, the oxygen atoms on the nitrate (N03-) molecule are transferred to a reduced compound and N gas is produced. Organic carbon and ferrous iron (Fe2+), derived from the dissolution of minerals such as pyrite (FeS2) and glauconite (an iron aluminosilicate clay), can act as reducing substrates; these reduced chemical species are common in the marine and estuarine deposits in Southern Maryland. The spatial distribution of geologic units and their lithology (sediment type) has been used to create a map of the potential for denitrification of ground water in the surficial aquifer of the Coastal Plain in Southern Maryland.

Abatement of the antibiotic levofloxacin in a solar photoelectro-Fenton flow plant: Modeling the dissolved organic carbon concentration-time relationship.

PubMed

Coria, Gabriela; Pérez, Tzayam; Sirés, Ignasi; Brillas, Enric; Nava, José L

2018-05-01

The degradation of solutions of the antibiotic levofloxacin (LVN) in sulfate medium at pH 3.0 has been investigated at pre-pilot scale by solar photoelectro-Fenton (SPEF) process. The flow plant included an FM01-LC filter-press cell equipped with a Ti|Pt anode and a three-dimensional-like air-diffusion cathode, connected to a compound parabolic collector as photoreactor and a continuous stirred tank under recirculation batch mode. The effect of volumetric flow rate on H 2 O 2 electrogeneration from O 2 reduction was assessed. Then, the influence of initial LVN concentration and Fe 2+ concentration as catalyst on dissolved organic carbon (DOC) removal was thoroughly investigated. LVN was gradually mineralized by SPEF process, with faster DOC abatement at 0.50 mM Fe 2+ , yielding 100% after 360 min at applied cathodic potential of -0.30 V|SHE. The high mineralization current efficiency (MCE) and low specific energy consumption (EC DOC ) revealed the extraordinary role of homogeneous hydroxyl radicals and natural UV light, which allowed the degradation of the antibiotic and its by-products with MCE values greater than 100%. Five cyclic by-products, N,N-diethylformamide and three short-chain linear carboxylic acids were detected by GC-MS and HPLC analyses. A parametric model to simulate the DOC decay versus electrolysis time was implemented for the SPEF pre-pilot flow plant, showing good agreement with experimental data. Copyright © 2018 Elsevier Ltd. All rights reserved.

The Use of Flow-Injection Analysis with Chemiluminescence Detection of Aqueous Ferrous Iron in Waters Containing High Concentrations of Organic Compounds

PubMed Central

Borman, Christopher J.; Sullivan, B. Patrick; Eggleston, Carrick M.; Colberg, Patricia J. S.

2009-01-01

An evaluation of flow-injection analysis with chemiluminescence detection (FIA-CL) to quantify Fe2+(aq) in freshwaters was performed. Iron-coordinating and/or iron-reducing compounds, dissolved organic matter (DOM), and samples from two natural water systems were used to amend standard solutions of Fe2+(aq). Slopes of the response curves from ferrous iron standards (1 – 100 nM) were compared to the response curves of iron standards containing the amendments. Results suggest that FIA-CL is not suitable for systems containing ascorbate, hydroxylamine, cysteine or DOM. Little or no change in sensitivity occurred in solutions of oxalate and glycine or in natural waters with little organic matter. PMID:22408532

Arsenic incorporation into FeS 2 pyrite and its influence on dissolution: A DFT study

NASA Astrophysics Data System (ADS)

Blanchard, Marc; Alfredsson, Maria; Brodholt, John; Wright, Kate; Catlow, C. Richard A.

2007-02-01

FeS 2 pyrite can incorporate large amounts of arsenic (up to ca. 10 wt%) and hence has a strong impact on the mobility of this toxic metalloid. Focussing on the lowest arsenic concentrations for which the incorporation occurs in solid solution, the substitution mechanisms involved have been investigated by assuming simple incorporation reactions in both oxidising and reducing conditions. The solution energies were calculated by Density Functional Theory (DFT) calculations and we predict that the formation of AsS dianion groups is the most energetically favourable mechanism. The results also suggest that the presence of arsenic will accelerate the dissolution and thus the generation of acid drainage, when the crystal dissolves in oxidising conditions.

Investigating vibrational anharmonic couplings in cyanide-bridged transition metal mixed valence complexes using two-dimensional infrared spectroscopy.

PubMed

Slenkamp, Karla M; Lynch, Michael S; Van Kuiken, Benjamin E; Brookes, Jennifer F; Bannan, Caitlin C; Daifuku, Stephanie L; Khalil, Munira

2014-02-28

Using polarization-selective two-dimensional infrared (2D IR) spectroscopy, we measure anharmonic couplings and angles between the transition dipole moments of the four cyanide stretching (νCN) vibrations found in [(NH3)5Ru(III)NCFe(II)(CN)5](-) (FeRu) dissolved in D2O and formamide and [(NC)5Fe(II)CNPt(IV)(NH3)4NCFe(II)(CN)5](4-) (FePtFe) dissolved in D2O. These cyanide-bridged transition metal complexes serve as model systems for studying the role of high frequency vibrational modes in ultrafast photoinduced charge transfer reactions. Here, we focus on the spectroscopy of the νCN modes in the electronic ground state. The FTIR spectra of the νCN modes of the bimetallic and trimetallic systems are strikingly different in terms of frequencies, amplitudes, and lineshapes. The experimental 2D IR spectra of FeRu and FePtFe and their fits reveal a set of weakly coupled anharmonic νCN modes. The vibrational mode anharmonicities of the individual νCN modes range from 14 to 28 cm(-1). The mixed-mode anharmonicities range from 2 to 14 cm(-1). In general, the bridging νCN mode is most weakly coupled to the radial νCN mode, which involves the terminal CN ligands. Measurement of the relative transition dipole moments of the four νCN modes reveal that the FeRu molecule is almost linear in solution when dissolved in formamide, but it assumes a bent geometry when dissolved in D2O. The νCN modes are modelled as bilinearly coupled anharmonic oscillators with an average coupling constant of 6 cm(-1). This study elucidates the role of the solvent in modulating the molecular geometry and the anharmonic vibrational couplings between the νCN modes in cyanide-bridged transition metal mixed valence complexes.

2015 Progress Report/July 2016: Iron Oxide Redox Transformation Pathways: The Bulk Electrical Conduction Mechanism

DOE Office of Scientific and Technical Information (OSTI.GOV)

Scherer, Michelle M.; Rosso, Kevin M.

Despite decades of research on the reactivity and stable isotope properties of Fe oxides, the ability to describe the redox behavior of Fe oxides in the environment is still quite limited. This is due, in large part, to the analytical and spatial complexities associated with studying microscopic processes at the Fe oxide-water interface. This project had the long-term vision of filling this gap by developing a detailed understanding of the relationship between interfacial ET processes, surface structure and charge, and mineral semiconducting properties. We focused on the Fe(III)-oxides and oxyhydroxides because of their geochemical preponderance, versatility in synthesis of compositionally,more » structurally, and morphologically tailored phases, and because they are amenable to a wide range of surface and bulk properties characterization. In particular, reductive transformation of phases such as hematite (α-Fe 2O 3) and goethite (α-FeOOH) in aqueous solution can serve as excellent model systems for studies of electron conduction processes, as well as provide valuable insights into effect of nanoscale conductive materials on contaminant fate at DOE sites. More specifically, the goal of the Iowa component of this project was to use stable Fe isotope measurements to simultaneously measure isotope specific oxidation states and concentrations of Fe at the hematite-water and goethite-water interface. This work builds on our previous work where we used an innovative combination of 57Fe Mössbauer spectroscopy and high precision isotope ratio measurements (MC-ICP-MS) to probe the dynamics of the reaction of aqueous Fe(II) with goethite. Mössbauer spectroscopy detects 57Fe only among all other Fe isotopes and we have capitalized on this to spectroscopically demonstrate Fe(II)-Fe(III) electron transfer between sorbed Fe(II) and Fe(III) oxides (Handler, et al., 2009; Gorski, et al. 2010; Rosso et al., 2010). By combining the Mössbauer spectroscopy and stable isotopes measurements, we have been able to simultaneously track the oxidation state and isotope concentration of the bulk Fe oxide and aqueous Fe. One of our most compelling findings is that despite the apparent stability of the Fe(II)-goethite system, there is actually a tremendous amount of Fe atom cycling occurring between the aqueous phase and the bulk goethite as indicated by the isotopic composition of both phases approaching the mass balance average (Handler et al., 2009). How such extensive re-crystallization and Fe atom exchange can occur with no significant morphological change is a fascinating question. Based on previous work from PI Rosso’s group showing that a potential gradient across hematite crystal faces leads to conduction through hematite and growth and dissolution at separate crystal faces we proposed that a redox-driven recrystallization could be occurring that would explain the extensive mixing observed with the isotope data. From our previous studies utilizing Mössbauer spectroscopy, we know that sorption of Fe(II) onto goethite results in electron transfer between the sorbed Fe(II) and the structural Fe(III) in goethite. Oxidation of the sorbed Fe(II) produces growth of goethite on goethite (i.e., homoepitaxy), as well as injection of an electron into goethite. It is possible that electron transfer from sorbed Fe(II) occurs across a potential gradient, and that Fe(II) atoms are dissolved at a different location on the goethite surface. These newly-reduced Fe(II) atoms could then dissolve into the aqueous phase, exposing fresh Fe(III) goethite to the aqueous phase. Through a repeated series of these five steps of sorption–electron transfer–crystal growth–conduction– dissolution, a redox-driven conveyor belt, could be established that would allow all of the goethite to be eventually exposed to the aqueous phase and exchanged. This surface-mediated recrystallization process would result in similar Fe isotope distributions in the aqueous phase and goethite particle, as we have observed here. It would also result in a stable aqueous Fe(II) concentration, if there were equal rates of goethite growth and dissolution.« less

Flavins secreted by roots of iron-deficient Beta vulgaris enable mining of ferric oxide via reductive mechanisms.

PubMed

Sisó-Terraza, Patricia; Rios, Juan J; Abadía, Javier; Abadía, Anunciación; Álvarez-Fernández, Ana

2016-01-01

Iron (Fe) is abundant in soils but generally poorly soluble. Plants, with the exception of Graminaceae, take up Fe using an Fe(III)-chelate reductase coupled to an Fe(II) transporter. Whether or not nongraminaceous species can convert scarcely soluble Fe(III) forms into soluble Fe forms has deserved little attention so far. We have used Beta vulgaris, one among the many species whose roots secrete flavins upon Fe deficiency, to study whether or not flavins are involved in Fe acquisition. Flavins secreted by Fe-deficient plants were removed from the nutrient solution, and plants were compared with Fe-sufficient plants and Fe-deficient plants without flavin removal. Solubilization of a scarcely soluble Fe(III)-oxide was assessed in the presence or absence of flavins, NADH (nicotinamide adenine dinucleotide, reduced form) or plant roots, and an Fe(II) trapping agent. The removal of flavins from the nutrient solution aggravated the Fe deficiency-induced leaf chlorosis. Flavins were able to dissolve an Fe(III)-oxide in the presence of NADH. The addition of extracellular flavins enabled roots of Fe-deficient plants to reductively dissolve an Fe(III)-oxide. We concluded that root-secretion of flavins improves Fe nutrition in B. vulgaris. Flavins allow B. vulgaris roots to mine Fe from Fe(III)-oxides via reductive mechanisms. © 2015 CSIC New Phytologist © 2015 New Phytologist Trust.

Effects of electron acceptors on soluble reactive phosphorus in the overlying water during algal decomposition.

PubMed

Wang, Jinzhi; Jiang, Xia; Zheng, Binghui; Niu, Yuan; Wang, Kun; Wang, Wenwen; Kardol, Paul

2015-12-01

Endogenous phosphorus (P) release from sediments is an important factor to cause eutrophication and, hence, algal bloom in lakes in China. Algal decomposition depletes dissolved oxygen (DO) and causes anaerobic conditions and therefore increases P release from sediments. As sediment P release is dependent on the iron (Fe) cycle, electron acceptors (e.g., NO3 (-), SO4 (2-), and Mn(4+)) can be utilized to suppress the reduction of Fe(3+) under anaerobic conditions and, as such, have the potential to impair the release of sediment P. Here, we used a laboratory experiment to test the effects of FeCl3, MnO2, and KNO3 on soluble reactive phosphorus (SRP) concentration and related chemical variables in the overlying water column during algal decomposition at different algal densities. Results showed that algal decomposition significantly depleted DO and thereby increased sediment Fe-bound P release. Compared with the control, addition of FeCl3 significantly decreased water SRP concentration through inhibiting sediment P release. Compared with FeCl3, addition of MnO2 has less potential to suppress sediment P release during algal decomposition. Algal decomposition has the potential for NO3 (-) removal from aquatic ecosystem through denitrification and by that alleviates the suppressing role of NO3 (-) on sediment P release. Our results indicated that FeCl3 and MnO2 could be efficient in reducing sediment P release during algal decomposition, with the strongest effect found for FeCl3; large amounts of NO3 (-) were removed from the aquatic ecosystem through denitrification during algal decomposition. Moreover, the amounts of NO3 (-) removal increased with increasing algal density.

Automation of high-frequency sampling of environmental waters for reactive species

NASA Astrophysics Data System (ADS)

Kim, H.; Bishop, J. K.; Wood, T.; Fung, I.; Fong, M.

2011-12-01

Trace metals, particularly iron and manganese, play a critical role in some ecosystems as a limiting factor to determine primary productivity, in geochemistry, especially redox chemistry as important electron donors and acceptors, and in aquatic environments as carriers of contaminant transport. Dynamics of trace metals are closely related to various hydrologic events such as rainfall. Storm flow triggers dramatic changes of both dissolved and particulate trace metals concentrations and affects other important environmental parameters linked to trace metal behavior such as dissolved organic carbon (DOC). To improve our understanding of behaviors of trace metals and underlying processes, water chemistry information must be collected for an adequately long period of time at higher frequency than conventional manual sampling (e.g. weekly, biweekly). In this study, we developed an automated sampling system to document the dynamics of trace metals, focusing on Fe and Mn, and DOC for a multiple-year high-frequency geochemistry time series in a small catchment, called Rivendell located at Angelo Coast Range Reserve, California. We are sampling ground and streamwater using the automated sampling system in daily-frequency and the condition of the site is substantially variable from season to season. The ranges of pH of ground and streamwater are pH 5 - 7 and pH 7.8 - 8.3, respectively. DOC is usually sub-ppm, but during rain events, it increases by an order of magnitude. The automated sampling system focuses on two aspects- 1) a modified design of sampler to improve sample integrity for trace metals and DOC and 2) remote controlling system to update sampling volume and timing according to hydrological conditions. To maintain sample integrity, the developed method employed gravity filtering using large volume syringes (140mL) and syringe filters connected to a set of polypropylene bottles and a borosilicate bottle via Teflon tubing. Without filtration, in a few days, the dissolved concentration of Fe and Mn in the ground and streamwater samples stored in low density polyethylene (LDPE) sample bags decreased by 89% and 97%, respectively. In some cases of groundwater, the concentration of Ca decreased by 25%, due to degassing of CO2. However, DOC of the samples in LDPE bags without filtration increased up to 50% in 2 weeks, suggesting contamination from the bag. Performance of the new design was evaluated using the Fe-Mn-spiked Rivendell samples and environmental water samples collected from 1) Rivendell, 2) the Strawberry Creek located at the University of California, Berkeley campus, and 3) the San Francisco Bay. The samples were filtered using the developed method and stored in room temperature in 2 - 3 weeks without further treatment. The method improved the sample integrity significantly; the average recovery rates of Fe, Mn, DOC, and Ca were 92%, 98%, 90%, and 97%, respectively.

Ground-water quality in east-central New Jersey, and a plan for sampling networks

USGS Publications Warehouse

Harriman, D.A.; Sargent, B.P.

1985-01-01

Groundwater quality was evaluated in seven confined aquifers and the water table aquifer in east-central New Jersey based on 237 analyses of samples collected in 1981-82, and 225 older analyses. Investigation of the effect of land use on water quality and several sampling network proposals for the region are reported. Generally, water in the confined aquifers is of satisfactory quality for human consumption and most other uses. Iron (Fe) and manganese (Mn) concentrations exceed U.S. EPA drinking water standards in some wells screened in the Potomac-Raritan-Magothy aquifer system. Sodium (Na) concentrations in samples from three wells more than 800 ft deep in the Englishtown aquifer exceed the standard. Iron and Mn concentrations in this aquifer may also exceed the standards. Iron concentrations in the Wenonah-Mount Laurel aquifer exceed the standard. Based on 15 analyses of water from the Vincetown aquifer, Mn is the only constituent that exceeds the drinking water standard. In the Manasquan aquifer, 4 of the 16 Na determinations exceed the standard, and 8 of 16 Fe determinations exceed the standard. Water quality in the Atlantic City 800-ft sand is generally satisfactory. However, 12 Fe and 1 of 12 Mn determinations exceed the standards. For the Rio Grande water-bearing zone, 1 of 3 Fe determinations exceed the standard. The Kirkwood-Cohansey aquifer system (the water table aquifer) was the most thoroughly sampled (249 chemical analyses from 209 wells). Dissolved solids, chloride, Fe, nitrate, and Mn concentrations exceed drinking water standards in some areas. The results of chi-square tests of constituent distributions based on analyses from 158 wells in the water table aquifer indicate that calcium is higher in industrial and commercial areas; and Mg, chloride, and nitrate-plus-nitrite is higher in residential areas. (Author 's abstract)

Low-oxygen and chemical kinetic constraints on the geochemical niche of neutrophilic iron(II) oxidizing microorganisms

NASA Astrophysics Data System (ADS)

Druschel, Gregory K.; Emerson, David; Sutka, R.; Suchecki, P.; Luther, George W., III

2008-07-01

Neutrophilic iron oxidizing bacteria (FeOB) must actively compete with rapid abiotic processes governing Fe(II) oxidation and as a result have adapted to primarily inhabit low-O 2 environments where they can more successfully compete with abiotic Fe(II) oxidation. The spatial distribution of these microorganisms can be observed through the chemical gradients they affect, as measured using in situ voltammetric analysis for dissolved Fe(II), Fe(III), O 2, and FeS (aq). Field and laboratory determination of the chemical environments inhabited by the FeOB were coupled with detailed kinetic competition studies for abiotic and biotic oxidation processes using a pure culture of FeOB to quantify the geochemical niche these organisms inhabit. In gradient culture tubes, the maximum oxygen levels, which were associated with growth bands of Sideroxydans lithotrophicus (ES-1, a novel FeOB), were 15-50 μM. Kinetic measurements made on S. lithotrophicus compared biotic/abiotic (killed control) Fe oxidation rates. The biotic rate can be a significant and measurable fraction of the total Fe oxidation rate below O 2 concentrations of approximately 50 μM, but biotic Fe(II) oxidation (via the biotic/abiotic rate comparison) becomes difficult to detect at higher O 2 levels. These results are further supported by observations of conditions supporting FeOB communities in field settings. Variablity in cell densities and cellular activity as well as variations in hydrous ferrous oxide mineral quantities significantly affect the laboratory kinetic rates. The microbial habitat (or geochemical niche) where FeOB are active is thus largely controlled by the competition between abiotic and biotic kinetics, which are dependent on Fe(II) concentration, P O2, temperature and pH in addition to the surface area of hydrous ferric oxide minerals and the cell density/activity of FeOB. Additional field and lab culture observations suggest a potentially important role for the iron-sulfide aqueous molecular cluster, FeS (aq), in the overall cycling of iron associated with the environments these microorganisms inhabit.

Chemical and Isotopic Characterization of Waters in Rio Tinto, Spain, Shows Possible Origin of the Blueberry Haematite Nodules in Meridiani Planum, Mars

NASA Astrophysics Data System (ADS)

Coleman, M. L.; Hubbard, C. G.; Mielke, R. E.; Black, S.

2005-12-01

Meridiani Planum sediments formed in an acid environment and include jarosite and other evaporitic sulfate minerals. Nodular spheroidal concretions appear to have grown in situ and are predominantly hematite. The source of the Rio Tinto, S. Spain, drains an area of extensive sulfide mineralization and is dominated by acid mine drainage processes. The system is not a Mars analog but potentially similar processes of sulfide oxidation produce sulfate rich waters which feed into the river and precipitate a large range of evaporitic sulfates including jarosite. Iron oxide minerals associated with the evaporites are either dispersed or bedded but not nodular. The water compositions appear to be mixtures of a few discreet end-members: the two most significant occur in undiluted form as inputs to the river and are relevant to many such systems. They both have all sulfur totally oxidized as sulfate. The first is a bright red water, pH ~1.5, Fe/S 0.5 and 23 g/L iron which is greater than 95% Fe3+. Its sulfate oxygen isotope composition is +2‰SMOW and about +7‰, relative to the water O isotope composition. These data indicate pyrite oxidation by Fe3+ with O in sulfate coming mainly from water. The second end-member is a pale green water, pH ~0.7, Fe/S 0.7, 50 g/L iron present mainly as Fe2+ and O isotope composition of sulfate about +6‰SMOW , about +12.5‰ relative to the water O value. Oxygen in sulfate comes mainly from atmospheric oxygen resulting from pyrite oxidation by molecular oxygen dissolved in water. Although the Rio Tinto system reactions probably are microbiologically mediated (relevant genera have been identified there) similar processes could occur abiotically but more slowly. Meridiani Planum sediments and nodules can be described by a plausible set of similar end-member processes. The primary source of sulfate is oxidation of sulfides present in basalt (pyrite, FeS2 or pyrrhotite, FeS) and weathering would have produced oxidized sulfate rich solutions at low pH. Ground water migration could produce evaporitic ponds where various bedded sulfate mineral sediments could form. The intergranular pore-spaces would be water filled. Most terrestrial spheroidal nodular concretions form by radial diffusion in pore-water of a chemical component of a very different oxidation state from that of the surrounding water. A nodular concretion is most usually formed by the reaction of the diffusive component with others in the pore-water. There are two main possible reaction sets for formation of the Blueberries that are consistent with all current data. 1. Local concentrations of organic matter (pre-biotic or biotic) formed reduction spots in which a small amount of Fe3+ either in solution or from evaporite mineral salts, was reduced to Fe2+ and then diffused radially to form an iron oxide nodule by reaction with inwardly diffusing dissolved oxygen. 2. Similar local concentrations of organic matter could also have engendered sulfate reduction and consequent outward diffusion of dissolved sulfide reacted with iron in solution to produce an iron sulfide nodule, subsequently oxidized in situ to hematite (maybe via goethite). Our current work is successfully identifying chemical and stable isotopic characteristics for both microbial and abiotic modes of all relevant reactions.

Acid-tolerant microaerophilic Fe(II)-oxidizing bacteria promote Fe(III)-accumulation in a fen.

PubMed

Lüdecke, Claudia; Reiche, Marco; Eusterhues, Karin; Nietzsche, Sandor; Küsel, Kirsten

2010-10-01

The ecological importance of Fe(II)-oxidizing bacteria (FeOB) at circumneutral pH is often masked in the presence of O(2) where rapid chemical oxidation of Fe(II) predominates. This study addresses the abundance, diversity and activity of microaerophilic FeOB in an acidic fen (pH ∼ 5) located in northern Bavaria, Germany. Mean O(2) penetration depth reached 16 cm where the highest dissolved Fe(II) concentrations (up to 140 µM) were present in soil water. Acid-tolerant FeOB cultivated in gradient tubes were most abundant (10(6) cells g(-1) peat) at the 10-20 cm depth interval. A stable enrichment culture was active at up to 29% O(2) saturation and Fe(III) accumulated 1.6 times faster than in abiotic controls. An acid-tolerant, microaerophilic isolate (strain CL21) was obtained which was closely related to the neutrophilic, lithoautotrophic FeOB Sideroxydans lithotrophicus strain LD-1. CL21 oxidized Fe(II) between pH 4 and 6.0, and produced nanoscale-goethites with a clearly lower mean coherence length (7 nm) perpendicular to the (110) plane than those formed abiotically (10 nm). Our results suggest that an acid-tolerant population of FeOB is thriving at redox interfaces formed by diffusion-limited O(2) transport in acidic peatlands. Furthermore, this well-adapted population is successfully competing with chemical oxidation and thereby playing an important role in the microbial iron cycle. © 2010 Society for Applied Microbiology and Blackwell Publishing Ltd.

The Effect of CaO on Gas/Slag/Matte/Tridymite Equilibria in Fayalite-Based Copper Smelting Slags at 1473 K (1200 °C) and P(SO2) = 0.25 Atm

NASA Astrophysics Data System (ADS)

Fallah-Mehrjardi, Ata; Hayes, Peter C.; Jak, Evgueni

2018-04-01

Fundamental experimental studies have been undertaken to determine the effect of CaO on the equilibria between the gas phase (CO/CO2/SO2/Ar) and slag/matte/tridymite phases in the Cu-Fe-O-S-Si-Ca system at 1473 K (1200 °C) and P(SO2) = 0.25 atm. The experimental methodology developed in the Pyrometallurgy Innovation Centre was used. New experimental data have been obtained for the four-phase equilibria system for fixed concentrations of CaO (up to 4 wt pct) in the slag phase as a function of copper concentration in matte, including the concentrations of dissolved sulfur and copper in slag, and Fe/SiO2 ratios in slag at tridymite saturation. The new data provided in the present study are of direct relevance to the pyrometallurgical processing of copper and will be used as an input to optimize the thermodynamic database for the copper-containing multi-component multi-phase system.

Chemical analyses of hot springs, pools, geysers, and surface waters from Yellowstone National Park, Wyoming, and vicinity, 1974-1975

USGS Publications Warehouse

Ball, James W.; Nordstrom, D. Kirk; Jenne, Everett A.; Vivit, Davison V.

1998-01-01

This report presents all analytical determinations for samples collected from Yellowstone National Park and vicinity during 1974 and 1975. Water temperature, pH, Eh, and dissolved O2 were determined on-site. Total alkalinity and F were determined on the day of sample collection. Flame atomic-absorption spectrometry was used to determine concentrations of Li, Na, K, Ca, and Mg. Ultraviolet/visible spectrophotometry was used to determine concentrations of Fe(II), Fe(III), As(III), and As(V). Direct-current plasma-optical-emission spectrometry was used to determine the concentrations of B, Ba, Cd, Cs, Cu, Mn, Ni, Pb, Rb, Sr, and Zn. Two samples collected from Yellowstone Park in June 1974 were used as reference samples for testing the plasma analytical method. Results of these tests demonstrate acceptable precision for all detectable elements. Charge imbalance calculations revealed a small number of samples that may have been subject to measurement errors in pH or alkalinity. These data represent some of the most complete analyses of Yellowstone waters available.

Biological versus mineralogical chromium reduction: potential for reoxidation by manganese oxide.

PubMed

Butler, Elizabeth C; Chen, Lixia; Hansel, Colleen M; Krumholz, Lee R; Elwood Madden, Andrew S; Lan, Ying

2015-11-01

Hexavalent chromium (Cr(vi), present predominantly as CrO4(2-) in water at neutral pH) is a common ground water pollutant, and reductive immobilization is a frequent remediation alternative. The Cr(iii) that forms upon microbial or abiotic reduction often co-precipitates with naturally present or added iron (Fe), and the stability of the resulting Fe-Cr precipitate is a function of its mineral properties. In this study, Fe-Cr solids were formed by microbial Cr(vi) reduction using Desulfovibrio vulgaris strain RCH1 in the presence of the Fe-bearing minerals hematite, aluminum substituted goethite (Al-goethite), and nontronite (NAu-2, Clay Minerals Society), or by abiotic Cr(vi) reduction by dithionite reduced NAu-2 or iron sulfide (FeS). The properties of the resulting Fe-Cr solids and their behavior upon exposure to the oxidant manganese (Mn) oxide (birnessite) differed significantly. In microcosms containing strain RCH1 and hematite or Al-goethite, there was significant initial loss of Cr(vi) in a pattern consistent with adsorption, and significant Cr(vi) was found in the resulting solids. The solid formed when Cr(vi) was reduced by FeS contained a high proportion of Cr(iii) and was poorly crystalline. In microcosms with strain RCH1 and hematite, Cr precipitates appeared to be concentrated in organic biofilms. Reaction between birnessite and the abiotically formed Cr(iii) solids led to production of significant dissolved Cr(vi) compared to the no-birnessite controls. This pattern was not observed in the solids generated by microbial Cr(vi) reduction, possibly due to re-reduction of any Cr(vi) generated upon oxidation by birnessite by active bacteria or microbial enzymes. The results of this study suggest that Fe-Cr precipitates formed in groundwater remediation may remain stable only in the presence of active anaerobic microbial reduction. If exposed to environmentally common Mn oxides such as birnessite in the absence of microbial activity, there is the potential for rapid (re)formation of dissolved Cr(vi) above regulatory levels.

Survival of the fittest: phosphorus burial in the sulfidic deep Black Sea

NASA Astrophysics Data System (ADS)

Kraal, Peter; Dijkstra, Nikki; Behrends, Thilo; Slomp, Caroline

2016-04-01

The Black Sea is characterized by permanently anoxic and sulfidic deep waters. Studies of the mechanisms of P burial in such a setting can be used to improve our understanding of P cycling in modern coastal systems undergoing eutrophication and ancient oceans during periods of anoxia in Earth's past. Here, we present phosphorus and iron (Fe) pools as determined in surface sediments along a transect from oxic shallow waters to sulfidic deep waters in the northwestern Black Sea, using a combination of bulk chemical analyses and micro-scale X-ray fluorescence (μXRF) and X-ray absorption spectroscopy (μXAS). We show that under oxic bottom water conditions, ferric iron oxides (Fe(III)ox) in surficial sediment efficiently scavenge dissolved phosphate from pore waters. Under these conditions, Fe(III)ox-bound P constitutes the main P pool at the sediment surface, but rapidly declines with depth in the sediment due to anoxic diagenesis. The transition from shallow (oxic) to deep (sulfidic) waters along the depth transect is reflected in a slight increase in the fraction of organic P. We also show evidence for authigenic calcium phosphate formation under sulfidic conditions at relatively low dissolved PO4 concentrations. Furthermore, we provide spectroscopic evidence for the presence of Fe(II)-Mn(II)-Mg-P minerals in sediments of the sulfidic deep basin. We hypothesize that these minerals are formed as a result of input of Fe(III)ox-P from shallower waters and subsequent transformation in either the water column or sediment. This finding suggests an unexpected strength of Fe-P shuttling from the shelf to the deep basin. While the presence of Fe-P species in such a highly sulfidic environment is remarkable, further analysis suggests that this P pool may not be quantitatively significant. In fact, our results indicate that some of the P that is interpreted as Fe-bound P based on chemical extraction may in fact be Ca-associated PO4 consisting of a combination of fish debris and adsorbed P.

Fe-As sludge stability and effluent quality for a two-stage As-contaminated water treatment with Fe(II) and aeration.

PubMed

Zhuang, J Ming; Hobenshield, Evan; Walsh, Tony

2009-02-01

A two-stage (I and II) lab-scale treatment system has been studied for arsenic removal from water using Fe(II) and lignosulphonates with aeration. In stage I, using an Fe/As mole ratio of 1.5-2.5 at a pH of around 6.5-7.5, the dissolved arsenic can be reduced with Fe(II) oxidation-precipitation from an initial 72 mg L(-1) to < 2 mg L(-1). The generated sludge is entirely recycled to the second tank of stage II. In the first tank of stage II, the water is further treated with the same amount of Fe(II) as that used in stage I, in the presence of lignosulphonates and aeration. The air-oxidization of Fe(II) to Fe(III) is continued for about 30 minutes at a pH of around 7.0-8.0. The water output from the first tank is transferred to the second tank in which mixing under aeration occurs with the sludge recycled from stage I. Accordingly, the dissolved arsenic in the effluent is reduced to < 0.1 mg L(-1). The results show that this two-stage process can save more than 50% of total chemical costs, and reduce the amount of sludge by more than 50%, in comparison with the conventional Fe(III)/lime-treatment process. According to US EPA regulations, the final Fe-As sludge is classified as non-hazardous materials by the Toxicity Characteristic Leaching Procedure. But, the study shows that the instability of Fe-As sludge could be influenced by some factors, such as higher pH levels, a longer water-leaching time and larger water-leaching volume, leading to the liberation of more dissolvable As species. After being treated with Ligmet stabilizer, the Fe-As sludge showed an improved stability under varying pH conditions and large amounts of water leaching. The treated Fe-As sludge is suitable for landfill disposal.

Fast Oxidation Processes in a Naturally Reduced Aquifer Zone Caused by Dissolved Oxygen

NASA Astrophysics Data System (ADS)

Davis, J. A.; Jemison, N. E.; Williams, K. H.; Hobson, C.; Bush, R. P.

2014-12-01

The occurrence of naturally reduced zones is quite common in alluvial aquifers in the western U.S.A. due to the burial of woody debris in flood plains. The naturally reduced zones are heterogeneously dispersed in such aquifers and are characterized by high concentrations of organic carbon and reduced phases, including iron sulfides and reduced forms of metals, including uranium(IV). The persistence of high concentrations of dissolved uranium(VI) at uranium-contaminated aquifers on the Colorado Plateau has been attributed to slow oxidation of insoluble uranium(IV) mineral phases that are found in association with these natural reducing zones, although there is little understanding of the relative importance of various potential oxidants. Three field experiments were conducted within an alluvial aquifer adjacent to the Colorado River near Rifle, CO wherein groundwater associated with naturally reduced zones was pumped into a gas-impermeable tank, mixed with a conservative tracer (Br-), bubbled with a gas phase composed of 97% O2 and 3% CO2, and then returned to the subsurface in the same well from which it was withdrawn. Within minutes of re-injection of the oxygenated groundwater, dissolved uranium(VI) concentrations increased from less than 1 μM to greater than 2.5 μM, demonstrating that oxygen can be an important oxidant for uranium in these field systems if supplied to the naturally reduced zones. Small concentrations of nitrate were also observed in the previously nitrate-free groundwater, and Fe(II) decreased to the detection limit. These results contrast with other laboratory and field results in which oxygen was introduced to systems containing high concentrations of mackinawite (FeS) rather than the more crystalline iron sulfides found in aged, naturally reduced zones. The flux of oxygen to the naturally reduced zones in the alluvial aquifers occurs mainly through interactions between groundwater and gas phases at the water table, and seasonal variations of the water table at the Rifle, CO site may play an important role in introducing oxygen into the system. Although oxygen was introduced directly to the naturally reduced zones in these experiments, delivery of oxidants to the system may normally be controlled by other oxidative pathways in which oxygen plays an indirect role.

Thermodynamic Simulation of Carbonate Cements-Water-Carbon Dioxide Equilibrium in Sandstone for Prediction of Precipitation/Dissolution of Carbonate Cements

PubMed Central

Zhong, Xinyan; Shang, Ruishu; Huang, Lihong

2016-01-01

Carbonate cements, such as calcite, dolomite, ferrocalcite and ankerite, play important roles in the formation of pores in sandstones: precipitation of carbonate cements modifies pores and inhibits compaction, while dissolution creates secondary pores. This work proposed a precipitation-dissolution model for carbonate cements-CO2-H2O system by means of ion equilibrium concentration ([M2+], M = Ca, Mg, Fe or Mn) with different factors, such as temperature, depth, pH, PCO2, variable rock composition and overpressure. Precipitation-dissolution reaction routes were also analyzed by minimization of the total Gibbs free energy (ΔG). Δ[M2+], the variation of [Ca2+], [Fe2+], [Mg2+] or [Mn2+] for every 100 m of burial depths, is used to predict precipitation or dissolution. The calculation results indicate that the increasing temperature results in decrease of equilibrium constant of reactions, while the increasing pressure results in a relatively smaller increase of equilibrium constant; As a result, with increasing burial depth, which brings about increase of both temperature and pressure, carbonate cements dissolve firstly and produces the maximal dissolved amounts, and then precipitation happens with further increasing depth; For example, calcite is dissolving from 0.0 km to 3.0 km with a maximal value of [Ca2+] at depth of 0.8 km, and then precipitates with depth deeper than 3.0 km. Meanwhile, with an increasing CO2 mole fraction in the gaseous phase from 0.1% to 10.0% in carbonate systems, the aqueous concentration of metal ions increases, e.g., dissolved amount of CaFe0.7Mg0.3(CO3)2 increases and reaches maximum of 1.78 mmol·L-1 and 8.26 mmol·L-1 at burial depth of 0.7 km with CO2 mole fraction of 0.1% and 10.0%, respectively. For the influence of overpressure in the calcite system, with overpressure ranging from 36 MPa to 83 MPa, pH reaches a minimum of 6.8 at overpressure of 51 MPa; meanwhile, Δ[Ca2+] increases slightly from -2.24 mmol·L-1 to -2.17 mmol·L-1 and remains negative, indicating it is also a precipitation process at burial depth of 3.9 km where overpressure generated. The method used in this study can be applied in assessing burial precipitation-dissolution processes and predicting possible pores in reservoirs with carbonate cement-water-carbon dioxide. PMID:27907043

Thermodynamic Simulation of Carbonate Cements-Water-Carbon Dioxide Equilibrium in Sandstone for Prediction of Precipitation/Dissolution of Carbonate Cements.

PubMed

Duan, Yiping; Feng, Mingshi; Zhong, Xinyan; Shang, Ruishu; Huang, Lihong

2016-01-01

Carbonate cements, such as calcite, dolomite, ferrocalcite and ankerite, play important roles in the formation of pores in sandstones: precipitation of carbonate cements modifies pores and inhibits compaction, while dissolution creates secondary pores. This work proposed a precipitation-dissolution model for carbonate cements-CO2-H2O system by means of ion equilibrium concentration ([M2+], M = Ca, Mg, Fe or Mn) with different factors, such as temperature, depth, pH, [Formula: see text], variable rock composition and overpressure. Precipitation-dissolution reaction routes were also analyzed by minimization of the total Gibbs free energy (ΔG). Δ[M2+], the variation of [Ca2+], [Fe2+], [Mg2+] or [Mn2+] for every 100 m of burial depths, is used to predict precipitation or dissolution. The calculation results indicate that the increasing temperature results in decrease of equilibrium constant of reactions, while the increasing pressure results in a relatively smaller increase of equilibrium constant; As a result, with increasing burial depth, which brings about increase of both temperature and pressure, carbonate cements dissolve firstly and produces the maximal dissolved amounts, and then precipitation happens with further increasing depth; For example, calcite is dissolving from 0.0 km to 3.0 km with a maximal value of [Ca2+] at depth of 0.8 km, and then precipitates with depth deeper than 3.0 km. Meanwhile, with an increasing CO2 mole fraction in the gaseous phase from 0.1% to 10.0% in carbonate systems, the aqueous concentration of metal ions increases, e.g., dissolved amount of CaFe0.7Mg0.3(CO3)2 increases and reaches maximum of 1.78 mmol·L-1 and 8.26 mmol·L-1 at burial depth of 0.7 km with CO2 mole fraction of 0.1% and 10.0%, respectively. For the influence of overpressure in the calcite system, with overpressure ranging from 36 MPa to 83 MPa, pH reaches a minimum of 6.8 at overpressure of 51 MPa; meanwhile, Δ[Ca2+] increases slightly from -2.24 mmol·L-1 to -2.17 mmol·L-1 and remains negative, indicating it is also a precipitation process at burial depth of 3.9 km where overpressure generated. The method used in this study can be applied in assessing burial precipitation-dissolution processes and predicting possible pores in reservoirs with carbonate cement-water-carbon dioxide.

Net acidity indicates the whole effluent toxicity of pH and dissolved metals in metalliferous saline waters.

PubMed

Degens, Bradley P; Krassoi, Rick; Galvin, Lynette; Reynolds, Brad; Micevska, Tina

2018-05-01

Measurements of potential acidity in water are used to manage aquatic toxicity risks of discharge from acid sulfate soils or acid mine drainage. Net acidity calculated from pH, dissolved metals and alkalinity is a common measurement of potential acidity but the relevance of current risk thresholds to aquatic organisms are unclear. Aquatic toxicity testing was carried out using four halophytic organisms with water from four saline sources in southern Western Australia (3 acidic drains and one alkaline river; 39-40 g TDS/L) where acidity was varied by adjusting pH to 4.5-6.5. The test species were brine shrimps (Artemia salina), locally sourced ostracods (Platycypris baueri), microalgae (Dunaliella salina) and amphipods (Allorchestes compressa). Testing found the EC 10 and IC 10 of net acidity ranged from -7.8 to 10.5 mg CaCO 3 /L with no survival or growth of any species at >47 mg CaCO 3 /L. Reduced net acidity indicated reduced whole effluent toxicity more reliably than increased pH alone with organisms tolerating pH up to 1.1 units lower in the absence of dissolved metals. Variation in toxicity indicated by net acidity was mostly attributed to reduced concentrations of dissolved Al and Fe combined with higher pH and alkalinity and some changes in speciation of Al and Fe with pH. These results indicate that rapid in-field assessments of net acidity in acidic, Al dominated waters may be an indicator of potential acute and sub-chronic impacts on aquatic organisms. Crown Copyright © 2018. Published by Elsevier Ltd. All rights reserved.

Development of a SREX Flowsheet for the Separation of Strontium from Dissolved INEEL Zirconium Calcine

DOE Office of Scientific and Technical Information (OSTI.GOV)

Law, Jack Douglas; Wood, David James; Todd, Terry Allen

1999-02-01

Laboratory experimentation has indicated that the SREX process is effective for partitioning 90 Sr from acidic radioactive waste solutions located at the Idaho Nuclear Technology and Engineering Center. These laboratory results were used to develop a flowsheet for countercurrent testing of the SREX process with dissolved pilot plant calcine. Testing was performed using 24 stages of 2-cm diameter centrifugal contactors which are installed in the Remote Analytical Laboratory hot cell. Dissolved Run #64 pilot plant calcine spiked with 85 Sr was used as feed solution for the testing. The flowsheet tested consisted of an extraction section (0.15 M 4',4'(5')-di-(tert-butylcyclohexo)-18-crown-6 andmore » 1.5 M TBP in Isopar-L.), a 1.0 M NaNO3 scrub section to remove extracted K from the SREX solvent, a 0.01 M HNO3 strip section for the removal of Sr from the SREX solvent, a 0.25 M Na2CO3 wash section to remove degradation products from the solvent, and a 0.1 M HNO3 rinse section. The behavior of 85 Sr, Na, K, Al, B, Ca, Cr, Fe, Ni, and Zr was evaluated. The described flowsheet successfully extracted 85 Sr from the dissolved pilot plant calcine with a removal efficiency of 99.6%. Distribution coefficients for 85 Sr ranged from 3.6 to 4.5 in the extraction section. With these distribution coefficients a removal efficiency of approximately >99.99% was expected. It was determined that the lower than expected removal efficiency can be attributed to a stage efficiency of only 60% in the extraction section. Extracted K was effectively scrubbed from the SREX solvent with the 1.0 M NaNO3 resulting in only 6.4% of the K in the HLW strip product. Sodium was not extracted from the dissolved calcine by the SREX solvent; however, the use of a 1.0 M NaNO3 scrub solution resulted in a Na concentration of 70 mg/L (12.3% of the feed concentration) in the HLW strip product. Al, B, Ca, Cr, Fe, Ni, and Zr were determined to be essentially inextractable.« less

Development of a SREX flowsheet for the separation of strontium from dissolved INEEL zirconium calcine

DOE Office of Scientific and Technical Information (OSTI.GOV)

Law, J.D.; Wood, D.J.; Todd, T.A.

1999-01-01

Laboratory experimentation has indicated that the SREX process is effective for partitioning {sup 90}Sr from acidic radioactive waste solutions located at the Idaho Nuclear Technology and Engineering Center. These laboratory results were used to develop a flowsheet for countercurrent testing of the SREX process with dissolved pilot plant calcine. Testing was performed using 24 stages of 2-cm diameter centrifugal contactors which are installed in the Remote Analytical Laboratory hot cell. Dissolved Run No.64 pilot plant calcine spiked with {sup 85}Sr was used as feed solution for the testing. The flowsheet tested consisted of an extraction section (0.15 M 4{prime},4{prime}(5{prime})-di-(tert-butylcyclohexo)-18-crown-6 andmore » 1.5 M TBP in Isopar-L.), a 1.0 M NaNO{sub 3} scrub section to remove extracted K from the SREX solvent, a 0.01 M HNO{sub 3} strip section for the removal of Sr from the SREX solvent, a 0.25 M Na2CO{sub 3} wash section to remove degradation products from the solvent, and a 0.1 M HNO{sub 3} rinse section. The behavior of {sup 85}Sr, Na, K, Al, B, Ca, Cr, Fe, Ni, and Zr was evaluated. The described flowsheet successfully extracted {sup 85}Sr from the dissolved pilot plant calcine with a removal efficiency of 99.6%. Distribution coefficients for {sup 85}Sr ranged from 3.6 to 4.5 in the extraction section. With these distribution coefficients a removal efficiency of approximately >99.99% was expected. It was determined that the lower than expected removal efficiency can be attributed to a stage efficiency of only 60% in the extraction section. Extracted K was effectively scrubbed from the SREX solvent with the 1.0 M NaNO{sub 3} resulting in only 6.4% of the K in the HLW strip product. Sodium was not extracted from the dissolved calcine by the SREX solvent; however, the use of a 1.0 M NaNO{sub 3} scrub solution resulted in a Na concentration of 70 mg/L (12.3% of the feed concentration) in the HLW strip product. Al, B, Ca, Cr, Fe, Ni, and Zr were determined to be essentially inextractable.« less

Element remobilization, "internal P-loading," and sediment-P reactivity researched by DGT (diffusive gradients in thin films) technique.

PubMed

Wu, Zhihao; Wang, Shengrui; He, Mengchang; Zhang, Li; Jiao, Lixin

2015-10-01

Labile P, Fe, and sulfide with the high spatial resolution in sediment porewater of five sites (A-E) of Dianchi Lake (China) were measured at same locations using AgI/Chelex-100, Chelex-100, and ferrihydrite DGT (diffusive gradients in thin films) probes. DGT derived P/Fe/S concentrations in sediment porewater on millimeter or sub-millimeter scale in order to reveal the element remobilization process and the mechanism of "internal P-loading" of sediments in Dianchi Lake. Decomposition of alga biomass in the uppermost sediment layer and the reductive dissolution of Fe-bound P in the anoxic sediment were the two main processes causing P release. A dynamic numerical model-DIFS (DGT-induced flux in sediments) was used to assess sediment-P reactivity (capacity of solid pool and rate of transfer) and P release risk by kinetic parameter-T C (1089∼20,450 s), distribution coefficient-K d (167.09∼502.0 cm(3) g(-1)), resupply parameter-R (from 0.242 to 0.518), and changes of dissolved/sorbed concentration, R and M at the microzone of DGT/porewater/sediment.

Structural stability of coprecipitated natural organic matter and ferric iron under reducing conditions

USGS Publications Warehouse

Henneberry, Yumiko K.; Kraus, Tamara E.C.; Nico, Peter S.; Horwath, William R.

2012-01-01

The objective was to assess the interaction of Fe coprecipitated with dissolved organic matter (DOM) and its effect on Fe (hydr)oxide crystallinity and DOM retention under abiotic reducing conditions. A Fe-based coagulant was reacted with DOM from an agricultural drain and the resulting precipitate (floc) was exposed to S(-II) and Fe(II). Solution concentrations of Fe(II/III) and DOM were monitored, floc crystallinity was determined using X-ray diffraction, and the composition and distribution of functional groups were assessed using scanning transmission X-ray microscopy (STXM) and near edge X-ray absorption fine structure (NEXAFS) spectroscopy. Results indicate coprecipitation of Fe(III) with DOM forms a non-crystalline floc that withstands crystallization regardless of change in pH, Fe:DOM ratio and type of reductant added. There was no evidence that exposure to reducing conditions led to release of DOM from the floc, indicating that coprecipitation with complex natural DOM in aquatic environments may stabilize Fe (hydr)oxides against crystallization upon reaction with reduced species and lead to long term sequestration of the DOM. STXM analysis identified spatially distinct regions with remarkable functional group purity, contrary to the model of DOM as a relatively uniform complex polymer lacking identifiable organic compounds. Polysaccharide-like OM was strongly and directly correlated with the presence of Fe but showed different Fe binding strength depending on the presence of carboxylic acid functional groups, whereas amide and aromatic functional groups were inversely correlated with Fe content.

Radionuclides in ground water of the Carson River Basin, western Nevada and eastern California, U.S.A.

USGS Publications Warehouse

Thomas, J.M.; Welch, A.H.; Lico, M.S.; Hughes, J.L.; Whitney, R.

1993-01-01

Ground water is the main source of domestic and public supply in the Carson River Basin. Ground water originates as precipitation primarily in the Sierra Nevada in the western part of Carson and Eagle Valleys, and flows down gradient in the direction of the Carson River through Dayton and Churchill Valleys to a terminal sink in the Carson Desert. Because radionuclides dissolved in ground water can pose a threat to human health, the distribution and sources of several naturally occurring radionuclides that contribute to gross-alpha and gross-beta activities in the study area were investigated. Generally, alpha and beta activities and U concentration increase from the up-gradient to down-gradient hydrographic areas of the Carson River Basin, whereas 222Rn concentration decreases. Both 226Ra and 228Ra concentrations are similar throughout the study area. Alpha and beta activities and U concentration commonly exceed 100 pCi/l in the Carson Desert at the distal end of the flow system. Radon-222 commonly exceeds 2,000 pCi/l in the western part of Carson and Eagle Valleys adjacent to the Sierra Nevada. Radium-226 and 228Ra concentrations are <5 pCi/l. Four ground water samples were analyzed for 210Po and one sample contained a high concentration of 21 pCi/l. Seven samples were analyzed for 210Pb; six contained <3 pCi/l and one contained 12 pCi/l. Thorium-230 was detected at concentrations of 0.15 and 0.20 pCi/l in two of four samples. Alpha-emitting radionuclides in the ground water originated from the dissolution of U-rich granitic rocks in the Sierra Nevada by CO2, oxygenated water. Dissolution of primary minerals, mainly titanite (sphene) in the granitic rocks, releases U to the water. Dissolved U is probably removed from the water by adsorption on Fe- and Mn-oxide coatings on fracture surfaces and fine-grained sediment, by adsorption on organic matter, and by coprecipitation with Fe and Mn oxides. These coated sediments are transported throughout the basin by fluvial processes. Thus, U is transported as dissolved and adsorbed species. A rise in the water table in the Carson Desert because of irrigation has resulted in the oxidation of U-rich organic matter and dissolution of U-bearing coatings on sediments, producing unusually high U concentration in the ground water. Alpha activity in the ground water is almost entirely from the decay of U dissolved in the water. Beta activity in ground water samples is primarily from the decay of 40K dissolved in the water and ingrowth of 238U progeny in the sample before analysis. Approximately one-half of the measured beta activity may not be present in ground water in the aquifer, but instead is produced in the sample after collection and before analysis. Potassium-40 is primarily from the dissolution of K-containing minerals, probably K-feldspar and biotite. Radon-222 is primarily from the decay of 226Ra in the aquifer materials. Radium in the ground water is thought to be mainly from alpha recoil associated with the decay of Th in the aquifer material. Some Ra may be from dissolution (or desorption) or Ra-rich coatings on sediments. ?? 1993.

Decrease of concentration and colloidal fraction of organic carbon and trace elements in response to the anomalously hot summer 2010 in a humic boreal lake.

PubMed

Shirokova, L S; Pokrovsky, O S; Moreva, O Yu; Chupakov, A V; Zabelina, S A; Klimov, S I; Shorina, N V; Vorobieva, T Ya

2013-10-01

The colloidal distribution and size fractionation of organic carbon (OC), major elements and trace elements (TE) were studied in a seasonally stratified, organic-rich boreal lake, Lake Svyatoe, located in the European subarctic zone (NW Russia, Arkhangelsk region). This study took place over the course of 4 years in both winter and summer periods using an in situ dialysis technique (1 kDa, 10 kDa and 50 kDa) and traditional frontal filtration and ultrafiltration (5, 0.22 and 0.025 μm). We observed a systematic difference in dissolved elements and colloidal fractions between summer and winter periods with the highest proportion of organic and organo-ferric colloids (1 kDa-0.22 μm) observed during winter periods. The anomalously hot summer of 2010 in European Russia produced surface water temperatures of approximately 30°C, which were 10° above the usual summer temperatures and brought about crucial changes in element speciation and size fractionation. In August 2010, the concentration of dissolved organic carbon (DOC) decreased by more than 30% compared to normal period, while the relative proportion of organic colloids decreased from 70-80% to only 20-30% over the full depth of the water column. Similarly, the proportion of colloidal Fe decreased from 90-98% in most summers and winters to approximately 60-70% in August 2010. During this hot summer, measurable and significant (>30% compared to other periods) decreases in the colloidal fractions of Ca, Mg, Sr, Ba, Al, Ti, Ni, As, V, Co, Y, all rare earth elements (REEs), Zr, Hf, Th and U were also observed. In addition, dissolved (<0.22 μm) TE concentrations decreased by a factor of 2 to 6 compared to previously investigated periods. The three processes most likely responsible for such a crucial change in element biogeochemistry with elevated water temperature are 1) massive phytoplankton bloom, 2) enhanced mineralization (respiration) of allochthonous dissolved organic matter by heterotrophic aerobic bacterioplankton and 3) photo-degradation of DOM and photo-chemical liberation of organic-bound TE. While the first process may have caused significant decreases in the total dissolved concentration of micronutrients (a factor of 2 to 5 for Cr, Mn, Fe, Ni, Cu, Zn and Cd and a factor of >100 for Co), the second and third factors could have brought about the decrease of allochthonous DOC concentration as well as the concentration and proportion of organic and organo-mineral colloidal forms of non-essential low-soluble trace elements present in the form of organic colloids (Al, Y, Ti, Zr, Hf, Th, Pb, all REEs). It can be hypothesized that climate warming in high latitudes capable of significantly raising surface water temperatures will produce a decrease in the colloidal fraction of most trace elements and, as a result, an increase in the most labile low molecular weight LMW(<1 kDa) fraction. Copyright © 2013 Elsevier B.V. All rights reserved.

A study of the capacitive deionisation performance under various operational conditions.

PubMed

Mossad, Mohamed; Zou, Linda

2012-04-30

Capacitive deionisation (CDI) has many advantages over other desalination technologies due to its low energy consumption, less environmental pollution and low fouling potential. The objectives of this study are to investigate the effect of operational conditions on the CDI electrosorption efficiency and energy consumption, to identify ion selectivity in multi-ionic solutions and to probe the effect of dissolved reactive silica on the treatment efficiency. A series of laboratory scale experiments were conducted using a CDI unit with activated carbon electrodes. The electrosorption removal efficiency was inversely related to solution temperature, initial total dissolved salts (TDS) concentration and the applied flow rate. CDI energy consumption (kWh/m(3)) is directly related to the TDS concentration and inversely related to the flow rate. The kinetics analysis indicated that the electrosorption followed pseudo-first-order kinetics model. Ion selectivity on activated carbon electrodes followed the order of Fe(3+)>Ca(2+)>Mg(2+)>Na(+) for cations and SO(4)(2-)>Br(-)>Cl(-)>F(-)>NO(3)(-) for anions. It was found that the dissolved silica was not removed by CDI; no silica fouling was found. The deterioration of activated carbon electrodes was not observed at any time during experiment. Copyright © 2012 Elsevier B.V. All rights reserved.

The chemistry of iron, aluminum, and dissolved organic material in three acidic, metal-enriched, mountain streams, as controlled by watershed and in-stream processes

USGS Publications Warehouse

McKnight, Diane M.; Bencala, Kenneth E.

1990-01-01

Several studies were conducted in three acidic, metal-enriched, mountain streams, and the results are discussed together in this paper to provide a synthesis of watershed and in-stream processes controlling Fe, Al, and DOC (dissolved organic carbon) concentrations. One of the streams, the Snake River, is naturally acidic; the other two, Peru Creek and St. Kevin Gulch, receive acid mine drainage. Analysis of stream water chemistry data for the acidic headwaters of the Snake River shows that some trace metal solutes (Al, Mn, Zn) are correlated with major ions, indicating that watershed processes control their concentrations. Once in the stream, biogeochemical processes can control transport if they occur over time scales comparable to those for hydrologic transport. Examples of the following in-stream reactions are presented: (1) photoreduction and dissolution of hydrous iron oxides in response to an experimental decrease in stream pH, (2) precipitation of Al at three stream confluences, and (3) sorption of dissolved organic material by hydrous iron and aluminum oxides in a stream confluence. The extent of these reactions is evaluated using conservative tracers and a transport model that includes storage in the substream zone.

Effect of dissimilatory iron and sulfate reduction on Arsenic dynamics in the wetland rhizosphere and its bioaccumulation in plants

NASA Astrophysics Data System (ADS)

Zhang, Zheyun; Moon, Hee Sun; Myneni, Satish; Jaffe, Peter

2015-04-01

Arsenic (As) pollution in water soil and sediments is of worldwide concern due to its ecological toxicity and chronic effects on human health. Wetlands are at the interface between ground and surface waters and because of their unique biogeochemical dynamics could be promising location for arsenic immobilization. However, the nature of biogeochemical reactions of As in wetlands are complex and not well understood. The dynamics of As in wetland sediments are closely linked to the redox cycling of Fe and S, both of which are affected by water-table fluctuations and wetland plants activity that are typical in such environments. Little is not known about redox cycling of Fe or S and their effects on As speciation, biogeochemical dynamics, and bioaccumulation in the wetland rhizosphere and plants. To gain further insights into these processes, twelve mesocosms were set up and planted with wetland plants (Scirpus actus), six were submerged in a tray (reactor) with ~ 170 mM SO4-2 and six in a tray with ~ 350 uM SO4-2 and two levels of ferrihydrite in the soil for each SO4-2 treatment. Each mesocosm was sealed and the only contact with the solution in the reactor was via the surface of the mesocosm. The mesocosms were run for 1.5 months to establish the plants, after which 50μM Na2HAsO4·7H2O was added to the reactors. Water in the reactors was constantly recirculated to make the solution homogeneous. The reactors were run for 4 months and monitored regularly for dissolved species, and were then dismantled. Results show that the presence of plants, high Fe, and high SO42- levels enhanced As sequestration in the soil. We hypothesize that the reason for this compounding effect is that plants release easily biodegradable organic carbon, which is used by microorganism to reduce ferrihydrite and SO42- to generate FeS or FeS2. More As is then sequestrated via sorption or co-precipitation on FeS or FeS2. Analysis of As in plant tissue showed that As uptake by Scirpus actus was mainly controlled by SO42- rather than Fe levels. When dissolved SO42 levels decreased from ~ 170 mM to ~ 350 uM, As concentrations in plant tissue increased by 97%, whereas no significant changes in plant As levels were seen for varying Fe concentrations in the soil. The As distribution in plant leaves and roots after 30 days of exposure to As was analyzed via Synchrotron X-ray fluorescence analyses. Compared with controls (no As addition), the uptake of As by plants was distributed along leaves veins for all plants exposed to As. The distribution of As in roots was correlated with the distribution of Fe in the roots, rather than with Ca or Zn, indicating that As may be co-distributed with Fe in plants.

Authigenesis of trace metals in energetic tropical shelf environments

USGS Publications Warehouse

Breckel, E.J.; Emerson, S.; Balistrieri, L.S.

2005-01-01

We evaluated authigenic changes of Fe, Mn, V, U, Mo, Cd and Re in suboxic, periodically remobilized, tropical shelf sediments from the Amazon continental shelf and the Gulf of Papua. The Cd/Al, Mo/Al, and U/Al ratios in Amazon shelf sediments were 82%, 37%, and 16% less than those in Amazon River suspended sediments, respectively. Very large depletions of U previously reported in this environment were not observed. The Cd/Al ratios in Gulf of Papua sediments were 76% lower than measurements made on several Papua New Guinea rivers, whereas U/Al ratios in the shelf sediments were enriched by approximately 20%. Other metal/Al ratios in the Papua New Guinea river suspended sediments and continental shelf sediments were not distinguishably different. Comparison of metal/Al ratios to grain size distributions in Gulf of Papua samples indicates that our observations cannot be attributed to differences in grain size between the river suspended sediments and continental shelf sediments. These two shelves constitute a source of dissolved Cd to the world ocean equal to 29-100% of the dissolved Cd input from rivers, but only 3% of the dissolved Mo input and 4% of the dissolved U input. Release of Cd, Mo, and U in tropical shelf sediments is likely a result of intense Fe and Mn oxide reduction in pore waters and resuspension of the sediments. Since we do not observe depletions of particulate Fe and Mn in the shelf sediments most of these dissolved metals must reoxidize in the overlying waters and reprecipitate. As Cd exhibits the largest losses on these tropical shelves, we examined the ability of newly formed Fe and Mn oxides to adsorb dissolved Cd using a geochemical diffuse double-layer surface complexation model and found the oxide surfaces are relatively ineffective at readsorbing Cd in seawater due to surface-site competition by Mg and Ca. If the remobilization and reoxidation of Fe and Mn occurs frequently enough before sediment is buried significant amounts of Cd may be removed from the oxide surfaces. Because a much greater percentage of Mn than Fe becomes remobilized in these shelf sediments, metals closely associated with Mn oxides (like Cd) are more likely to show losses during deposition. ?? 2005 Elsevier Ltd. All rights reserved.

The marine diatom and diazotroph under future climate: Role of Iron

NASA Astrophysics Data System (ADS)

Li, Xuefeng; Fonseca-batista, Debany; Brouwers, Julie; Roevros, Nathalie; Dehairs, Frank; Chou, Lei

2016-04-01

Diatoms constitute a major group of phytoplankton, accounting for one quarter of the world's net primary productivity. Diazotrophs provide the largest input of new nitrogen (N) to the ocean and control the marine N budgets. It has been shown that iron (Fe) can be the limiting factor for diatom growth, in particular, in the HNLC (High Nutrient Low Chlorophyll) regions. This trace element can also govern the development of marine diazotrophs due to the high Fe demand necessary for biological N2 fixation. Iron plays thus an essential role in governing the marine primary productivity and the efficiency of biological carbon pump. Ocean systems are undergoing continuous modifications at varying rates and magnitudes as a result of changing climate. The objectives of our research is to evaluate 1) how climate change (dust deposition, ocean warming and acidification) can affect Fe biogeochemistry and the growth of diatoms and diazotrophs, and 2) the role of Fe in the control of biological N2 fixation under future climate scenarios. Laboratory culture experiments using Chaetoceros socialis were examined at two temperatures (13°C and 18°C) and two CO2 conditions (400 μatm and 800 μatm). The present study demonstrates clearly the influence of ocean acidification on the release of Fe upon dust deposition. It also shows that dust particles could provide a readily utilizable source of Fe and other macronutrients (dissolved phosphate and silicate) for phytoplankton growth. Elevated pCO2 concentrations may have adverse impact on the diatom growth; seawater warming may cause poleward shifts in the biogeographic distribution of diatoms. The impact of Fe on the natural N2 fixation was tested via field incubation experiments using natureal phytoplankton assemblage in the Bay of Biscay and along the Iberian Margin. N2 fixation rates in oligotrophic waters were greatly stimulated through the addition of dissolved Fe compared to the control, demonstrating the limitation of N2 fixation by Fe. Numerous factors can affect the extent of N2 fixation, but a better understanding of the major controlling factors is highly required. Semi-continuous dilution culture experiments were conducted on Trichodesmium IMS-101 under future high pCO2 and warming seawater conditions. Additionally, special attention has been given to studying the effects of mineral dust deposition which is believed to promote N2 fixation through increasing Fe availability.

Toxicological responses of the hard clam Meretrix meretrix exposed to excess dissolved iron or challenged by Vibrio parahaemolyticus.

PubMed

Zhou, Qing; Zhang, Yong; Peng, Hui-Fang; Ke, Cai-Huan; Huang, He-Qing

2014-11-01

The responses of genes encoding defense components such as ferritin, the lipopolysaccharide-induced tumor necrosis factor-alpha factor (LITAF), the inhibitor of nuclear factor-κB (IκB), metallothionein, and glutathione peroxidase were assessed at the transcriptional level in order to investigate the toxicological and immune mechanism of the hard clam Meretrix meretrix (HCMM) following challenge with iron or a bacterium (Vibrio parahaemolyticus). Fe dissolved in natural seawater led to an increase of Fe content in both the hepatopancreas and gill tissue of HCMM between 4 and 15 days of exposure. The ferritin gene responded both transcriptionally as indicated by real-time quantitative PCR and translationally as shown by western blotting results to iron exposure and both transcriptional and translational ferritin expression in the hepatopancreas had a positive correlation with the concentration of dissolved iron in seawater. Both iron and V. parahaemolyticus exposure triggered immune responses with similar trends in clam tissues. There was a significant post-challenge mRNA expression of LITAF and IκB at 3h, ferritin at 24h, and metallothionein and glutathione peroxidase at 48h. This behavior might be linked to their specific functions in physiological processes. These results suggested that similar signaling pathways were triggered during both iron and V. parahaemolyticus challenges. Here, we indicated that the ferritin of Meretrix meretrix was an intermediate in the pathway of iron homeostasis and in its innate immune defense mechanism. Copyright © 2014 Elsevier B.V. All rights reserved.

Co-diagenesis of iron and phosphorus in hydrothermal sediments from the southern East Pacific Rise: Implications for the evaluation of paleoseawater phosphate concentrations

NASA Astrophysics Data System (ADS)

Poulton, Simon W.; Canfield, Donald E.

2006-12-01

We present a detailed study of the co-diagenesis of Fe and P in hydrothermal plume fallout sediments from ˜19°S on the southern East Pacific Rise. Three distal sediment cores from 340-1130 km from the ridge crest, collected during DSDP Leg 92, were analysed for solid phase Fe and P associations using sequential chemical extraction techniques. The sediments at all sites are enriched in hydrothermal Fe (oxyhydr)oxides, but during diagenesis a large proportion of the primary ferrihydrite precipitates are transformed to the more stable mineral form of goethite and to a lesser extent to clay minerals, resulting in the release to solution of scavenged P. However, a significant proportion of this P is retained within the sediment, by incorporation into secondary goethite, by precipitation as authigenic apatite, and by readsorption to Fe (oxyhydr)oxides. Molar P/Fe ratios for these sediments are significantly lower than those measured in plume particles from more northern localities along the southern East Pacific Rise, and show a distinct downcore decrease to a depth of ˜12 m. Molar P/Fe ratios are then relatively constant to a depth of ˜35 m. The Fe and P speciation data indicate that diagenetic modification of the sediments is largely complete by a depth of 2.5 m, and thus depth trends in molar P/Fe ratios can not solely be explained by losses of P from the sediment by diffusion to the overlying water column during early diagenesis. Instead, these sediments are likely recording changes in dissolved P concentrations off the SEPR, possibly as a result of redistribution of nutrients in response to changes in oceanic circulation over the last 10 million years. Furthermore, the relatively low molar P/Fe ratios observed throughout these sediments are not necessarily solely due to losses of scavenged P by diffusion to the overlying water column during diagenesis, but may also reflect post-depositional oxidation of pyrite originating from the volatile-rich vents of the southern East Pacific Rise. This study suggests that the molar P/Fe ratio of oxic Fe-rich sediments may serve as a proxy of relative changes in paleoseawater phosphate concentrations, particularly if Fe sulfide minerals are not an important component during transport and deposition.

Evaluating the potential of three Fe- and Mn-(nano)oxides for the stabilization of Cd, Cu and Pb in contaminated soils.

PubMed

Michálková, Zuzana; Komárek, Michael; Šillerová, Hana; Della Puppa, Loïc; Joussein, Emmanuel; Bordas, François; Vaněk, Aleš; Vaněk, Ondřej; Ettler, Vojtěch

2014-12-15

The potential of three Fe- and Mn-(nano)oxides for stabilizing Cd, Cu and Pb in contaminated soils was investigated using batch and column experiments, adsorption tests and tests of soil microbial activity. A novel synthetic amorphous Mn oxide (AMO), which was recently proposed as a stabilizing amendment, proved to be the most efficient in decreasing the mobility of the studied metals compared to nano-maghemite and nano-magnetite. Its application resulted in significant decreases of exchangeable metal fractions (92%, 92% and 93% decreases of Cd, Cu and Pb concentrations, respectively). The adsorption capacity of the AMO was an order of magnitude higher than those recorded for the other amendments. It was also the most efficient treatment for reducing Cu concentrations in the soil solution. No negative effects on soil microorganisms were recorded. On the other hand, the AMO was able to dissolve soil organic matter to some extent. Copyright © 2014 Elsevier Ltd. All rights reserved.

Degradation of hydraulic fracturing additive 2-butoxyethanol using heat activated persulfate in the presence of shale rock.

PubMed

Manz, Katherine E; Carter, Kimberly E

2018-09-01

Changes in fluid composition during hydraulic fracturing (HF) for natural gas production can impact well productivity and the water quality of the fluids returning to the surface during productivity. Shale formation conditions can influence the extent of fluid transformation. Oxidizers, such as sodium persulfate, likely play a strong role in fluid transformation. This study investigates the oxidation of 2-butoxyethanol (2-BE), a surfactant used in HF, by sodium persulfate in the presence of heat, pH changes, Fe(II), and shale rock. Increasing temperature and Fe(II) concentrations sped up 2-BE oxidation, while pH played little to no role in 2-BE degradation. The presence of shale rock impeded 2-BE oxidation with increasing shale concentrations causing decreasing pseudo-first-order reaction rate constant to be observed. Over the course of reactions containing shales, dissolved solids were tracked to better understand how reactions with minerals in the shale impact water quality. Copyright © 2018 Elsevier Ltd. All rights reserved.

Macroalgal biomonitors of trace metal contamination in acid sulfate soil aquaculture ponds.

PubMed

Gosavi, K; Sammut, J; Gifford, S; Jankowski, J

2004-05-25

Earthen shrimp aquaculture ponds are often impacted by acid sulfate soils (ASS), typically resulting in increased disease and mortality of cultured organisms. Production losses have been attributed to either low pH or to elevated concentrations of toxic metals, both direct products of pyrite oxidation in ASS. The standard farm management practice to minimise effects of pyrite oxidation is to maintain pH of pond waters above 5, based on the assumption that dissolved metal bioavailability is negligible at this pH. This study aimed to test the validity of this assumption, and therefore elucidate a possible role of toxic heavy metals in observed decreases in farm productivity. Metal bioaccumulation in four genera of macroalgae, Ulva sp., Enteromorpha sp., Cladophora sp. and Chaetomorpha sp., sampled from ASS-affected shrimp aquaculture ponds were measured using inductively coupled plasma-optical emission spectroscopy (ICP-OES) to assess the relative bioavailability of dissolved metals within the system. Results showed that all four genera of macroalgae accumulated appreciable quantities of Fe, Al, Zn, Cd, Cu, As and Pb. Iron and Al, the most common metals mobilised from ASS, were both accumulated in all algal genera to concentrations three orders of magnitude greater than all other metals analysed. These findings indicate that dissolved heavy metals are indeed bioavailable within the aquaculture pond system. A literature search of heavy metal bioaccumulation by these algal genera revealed concentrations recorded in this study are comparable to highly contaminated environments, such as those exposed to urban, industrial and mining pollution. The results of this study indicate that dissolved metal bioavailability in many earthen shrimp aquaculture ponds may be higher than previously thought.

Dissolution Behaviour of Hazardous Materials from Steel Slag with Wet Grinding Method

NASA Astrophysics Data System (ADS)

Hisyamudin Muhd Nor, Nik; Norhana Selamat, Siti; Hanif Abd Rashid, Muhammad; Fauzi Ahmad, Mohd; Jamian, Saifulnizan; Chee Kiong, Sia; Fahrul Hassan, Mohd; Mohamad, Fariza; Yokoyama, Seiji

2016-06-01

Steel slag is a by-product from steel industry and it contains variety of hazardous materials. In this study, the dissolution behaviour and removal potential of hazardous materials from steel slag with the wet grinding method was investigated. The slag was wet ground in the CO2 atmosphere and the slurry produced was filtered using centrifugal separator to separate the liquid and solid sediments. Then, the concentrations of dissolved metal elements in the liquid sediment were analyzed by ICP-MS. The changes of pH during the grinding were also investigated. It was found that the pHs were decreased immediately after the CO2 gas introduced into the vessel. The pHs were ranging from 6.8 to 7.6 at the end of grinding. The dissolved concentration of Zn and Cr were ranging from 5~45 [mg/dm3] and 0.2~2.5 [mg/dm3] respectively. The ratios of Zn removal for stainless steel oxidizing and reducing slag were very high, but those from normal steel oxidizing and reducing slag were very low. It is assumed that the Zn dissolved as ZnOH+ from Zn(OH)2 that formed due to the reaction between ZnO and water. Dissolution of Cr also occurred but in very low quantity compared to the dissolution of Zn. The dissolution of Cr occurred due to the grinding process and small amount of Cr(OH)3 was formed during the grinding. This small formation of Cr(OH)3 resulted to the low dissolved concentration of Cr in the form of Cr(OH)2+. According to the XRD analysis, the Cr mostly existed in the slags as Cr(IIl) in the form of MgCr2O4 and FeCr2O4.

Aggregate-scale heterogeneity in iron (hydr)oxide reductive transformations

DOE Office of Scientific and Technical Information (OSTI.GOV)

Tufano, K.J.; Benner, S.G.; Mayer, K.U.

There is growing awareness of the complexity of potential reaction pathways and the associated solid-phase transformations during the reduction of Fe (hydr)oxides, especially ferrihydrite. An important observation in static and advective-dominated systems is that microbially produced Fe(II) accelerates Ostwald ripening of ferrihydrite, thus promoting the formation of thermodynamically more stable ferric phases (lepidocrocite and goethite) and, at higher Fe(II) surface loadings, the precipitation of magnetite; high Fe(II) levels can also lead to green rust formation, and with high carbonate levels siderite may also be formed. This study expands this emerging conceptual model to a diffusion-dominated system that mimics an idealizedmore » micropore of a ferrihydrite-coated soil aggregate undergoing reduction. Using a novel diffusion cell, coupled with micro-x-ray fluorescence and absorption spectroscopies, we determined that diffusion-controlled gradients in Fe{sup 2+}{sub (aq)} result in a complex array of spatially distributed secondary mineral phases. At the diffusive pore entrance, where Fe{sup 2+} concentrations are highest, green rust and magnetite are the dominant secondary Fe (hydr)oxides (30 mol% Fe each). At intermediate distances from the inlet, green rust is not observed and the proportion of magnetite decreases from approximately 30 to <10%. Across this same transect, the proportion of goethite increases from undetectable up to >50%. At greater distances from the advective-diffusive boundary, goethite is the dominant phase, comprising between 40 and 95% of the Fe. In the presence of magnetite, lepidocrocite forms as a transient-intermediate phase during ferrihydrite-to-goethite conversion; in the absence of magnetite, conversion to goethite is more limited. These experimental observations, coupled with results of reactive transport modeling, confirm the conceptual model and illustrate the potential importance of diffusion-generated concentration gradients in dissolved Fe{sup 2+} on the fate of ferrihydrite during reduction in structured soils.« less

Weathering of the Rio Blanco Quartz Diorite, Luquillo Mountains, Puerto Rico: Coupling Oxidation, Dissolution, And Fracturing

DOE Office of Scientific and Technical Information (OSTI.GOV)

Buss, H.L.; Sak, P.B.; Webb, S.M.

2009-05-12

In the mountainous Rio Icacos watershed in northeastern Puerto Rico, quartz diorite bedrock weathers spheroidally, producing a 0.2-2 m thick zone of partially weathered rock layers ({approx}2.5 cm thickness each) called rindlets, which form concentric layers around corestones. Spheroidal fracturing has been modeled to occur when a weathering reaction with a positive {Delta}V of reaction builds up elastic strain energy. The rates of spheroidal fracturing and saprolite formation are therefore controlled by the rate of the weathering reaction. Chemical, petrographic, and spectroscopic evidence demonstrates that biotite oxidation is the most likely fracture-inducing reaction. This reaction occurs with an expansion inmore » d (0 0 1) from 10.0 to 10.5 {angstrom}, forming 'altered biotite'. Progressive biotite oxidation across the rindlet zone was inferred from thin sections and gradients in K and Fe(II). Using the gradient in Fe(II) and constraints based on cosmogenic age dates, we calculated a biotite oxidation reaction rate of 8.2 x 10{sup -14} mol biotite m{sup -2} s{sup -1}. Biotite oxidation was documented within the bedrock corestone by synchrotron X-ray microprobe fluorescence imaging and XANES. X-ray microprobe images of Fe(II) and Fe(III) at 2 {micro}m resolution revealed that oxidized zones within individual biotite crystals are the first evidence of alteration of the otherwise unaltered corestone. Fluids entering along fractures lead to the dissolution of plagioclase within the rindlet zone. Within 7 cm surrounding the rindlet-saprolite interface, hornblende dissolves to completion at a rate of 6.3 x 10{sup -13} mol hornblende m{sup -2} s{sup -1}: the fastest reported rate of hornblende weathering in the field. This rate is consistent with laboratory-derived hornblende dissolution rates. By revealing the coupling of these mineral weathering reactions to fracturing and porosity formation we are able to describe the process by which the quartz diorite bedrock disaggregates and forms saprolite. In the corestone, biotite oxidation induces spheroidal fracturing, facilitating the influx of fluids that react with other minerals, dissolving plagioclase and chlorite, creating additional porosity, and eventually dissolving hornblende and precipitating secondary minerals. The thickness of the resultant saprolite is maintained at steady state by a positive feedback between the denudation rate and the weathering advance rate driven by the concentration of pore water O{sub 2} at the bedrock-saprolite interface.« less

The effect of volcanic eruptions on the chemistry of surface waters: The 1991 and 2000 eruptions of Mt. Hekla, Iceland

NASA Astrophysics Data System (ADS)

Flaathen, Therese K.; Gislason, Sigurdur R.

2007-08-01

The Mt. Hekla eruptions in 1991 and 2000 have provided a unique opportunity to study the local environmental effects of high latitude volcanic eruptions in the middle of winter. Both eruptions started around sunset at sub-zero temperatures. In order to define better these effects we studied the chemistry of surface waters in the vicinity of the volcano. Additionally, we describe and predict the environmental consequences of these volcanic eruptions on the chemistry of surface waters on land and in the ocean. Several dissolved elements in the polluted snow melt from the 2000 eruption (Cl, F, Al, Fe, Mn, As, Cd, Pb, Zn, and U) exceeded the limits for water intended for human consumption. The volcanic ash, the primary minerals and secondary mineral phases that commonly form in the weathering environment of Iceland were undersaturated in the polluted snow melts with the exception of fluorite, barite, goethite and amorphous FeOOH. These minerals can constrain the maximum initial concentration of the respective dissolved constituents in the meltwaters. It took few days after the first rainfall on the volcanic ash to flush out the readily soluble constituents in the vicinity of the headwaters of the Ytri-Rangá River. The polluted river waters were oversaturated with respect to several secondary minerals, resulting in precipitation of amorphous Al hydroxide and FeOOH and further, scavenging of some trace elements on the Al and Fe surfaces. Dissolved Al and F were the main contaminants in the Ytri-Rangá river water. Previous studies have shown that combined Al-F toxicity is directly related to the predominance of specific Al-F species in solution. Model calculations for mixing of a Hekla-type volcanic cloud with 4 surface water end-members shows Al-F species to be most important in rain and dilute river waters. This makes Al and F phyto-available but diminishes the concentration of the Al 3+ species, the most toxic Al species. Mixing with high alkalinity river waters or seawater results in the domination of non toxic Al(OH) 4- species at dilutions greater than 800, thus hindering Al toxicity and bioavailability. This study indicates that H 2SO 4 contamination from volcanic eruptions is time and place dependent. Volcanic eruptions that take place during winter at high latitudes result in relatively high global sulfur contamination and relatively low local sulfur contamination due to the low oxidation rate of SO 2 into H 2SO 4 because of the low solar radiation.

Distribution characteristics of dissolved organic carbon in annular wetland soil-water solutions through soil profiles in the Sanjiang Plain, northeast China.

PubMed

Xi, Min; Lu, Xian-Guo; Li, Yue; Kong, Fan-Long

2007-01-01

Overwhelming evidence reveals that concentrations of dissolved organic carbon (DOC) have increased in streams which brings negative environmental impacts. DOC in stream flow is mainly originated from soil-water solutions of watershed. Wetlands prove to be the most sensitive areas as an important DOC reserve between terrestrial and fluvial biogeosystems. This reported study was focused on the distribution characteristics and the controlling factors of DOC in soil-water solutions of annular wetland, i.e., a dishing wetland and a forest wetland together, in the Sanjiang Plain, Northeast China. The results indicate that DOC concentrations in soil-water solutions decreased and then increased with increasing soil depth in the annular wetland. In the upper soil layers of 0-10 cm and 10-20 cm, DOC concentrations in soil-water solutions linearly increased from edge to center of the annular wetland (R2 = 0.3122 and R2 = 0.443). The distribution variations were intimately linked to DOC production and utilization and DOC transport processes in annular wetland soil-water solutions. The concentrations of total organic carbon (TOC), total carbon (TC) and Fe(II), DOC mobility and continuous vertical and lateral flow affected the distribution variations of DOC in soil-water solutions. The correlation coefficients between DOC concentrations and TOC, TC and Fe(II) were 0.974, 0.813 and 0.753 respectively. These distribution characteristics suggested a systematic response of the distribution variations of DOC in annular wetland soil-water solutions to the geometry of closed depressions on a scale of small catchments. However, the DOC in soil pore water of the annular wetland may be the potential source of DOC to stream flow on watershed scale. These observations also implied the fragmentation of wetland landscape could bring the spatial-temporal variations of DOC distribution and exports, which would bring negative environmental impacts in watersheds of the Sanjiang Plain.

Characterising microbial reduction of arsenate sorbed to ferrihydrite and its concurrence with iron reduction and the consequent impact on arsenic mobilisation

NASA Astrophysics Data System (ADS)

Huang, Jen-How

2014-05-01

Mobilisation of solid phase arsenic under reducing conditions involves a combination of microbial arsenate and iron reduction and is affected by secondary reactions of released products. A series of model anoxic incubations were performed to understand the concurrence between arsenate and ferrihydrite reduction by Shewanella putrefaciens strain CN-32 at different concentrations of arsenate, ferrihydrite and lactate, and with given ΔGrxn for arsenate and ferrihydrite reduction in non-growth conditions at pH 7. The reduction kinetics of arsenate sorbed to ferrihydrite is predominately controlled by the availability of dissolved arsenate, which is measured by the integral of dissolved arsenate concentrations against incubation time and shown to correlate with the first order rate constants. Thus, the mobilisation of adsorbed As(V) can be regarded as the rate determining step of microbial reduction of As(V) sorbed to ferrihydrite. High lactate concentrations slightly slowed down the rate of arsenate reduction due to the competition with arsenate for microbial contact. Under all experimental conditions, simultaneous arsenate and ferrihydrite reduction occurred following addition of S. putrefaciens inoculums and suggested no apparent competition between these two enzymatic reductions. Ferrous ions released from iron reduction might retard microbial arsenate reduction at high arsenate and ferrihydrite concentrations due to formation of ferrous arsenate. At high arsenate to ferrihydrite ratios, reductive dissolution of ferrihydrite shifted arsenate from sorption to dissolution and hence accelerated arsenate reduction. Reductive dissolution of ferrihydrite may cause additional releases of adsorbed As(V) into solution, which is especially effective at high As(V) to ferrihydrite ratios. In comparison, formation of Fe(II) secondary minerals during microbial Fe(III) reduction were responsible for trapping solution As(V) in the systems with high ferrihydrite but low As(V) concentrations. In summary, the interaction between microbial arsenate and ferrihydrite reduction did not correlate with ΔGrxn, but instead was governed by geochemical and microbial parameters, which may substantially influence the mobility of arsenic.

Microbes Enhance Mobility of Arsenic in Pleistocene Aquifer Sand from Bangladesh

PubMed Central

Dhar, Ratan K.; Zheng, Yan; Saltikov, Chad W.; Radloff, Kathleen A.; Mailloux, Brian; Ahmed, Kazi. M.; van Geen, Alexander

2018-01-01

Dissimilatory metal-reducing bacteria can mobilize As, but few studies have studied such processes in deeper orange-colored Pleistocene sands containing 1–2 mg kg−1 As that are associated with low-As groundwater in Bangladesh. To address this gap, anaerobic incubations were conducted in replicate over 90 days using natural orange sands initially containing 0.14 mg kg−1 of 1 M phosphate-extractable As (24 hr), >99% as As(V), and 0.8 g kg−1 of 1.2 M HCl-leachable Fe (1 hr at 80°C), 95% as Fe(III). The sediment was resuspended in artificial groundwater, with or without lactate as a labile carbon source, and inoculated with metal-reducing Shewanella sp. ANA-3. Within 23 days, dissolved As concentrations increased to 17 μg L−1 with lactate, 97% as As(III), and 2 μg L−1 without lactate. Phosphate-extractable As concentrations increased 4-fold to 0.6 mg kg−1 in the same incubations, even without the addition of lactate. Dissolved As levels in controls without Shewanella, both with and without lactate, instead remained <1 μg L−1. These observations indicate that metal-reducers such as Shewanella can trigger As release to groundwater by converting sedimentary As to a more mobilizable form without the addition of high levels of labile carbon. Such interactions need to be better understood to determine the vulnerability of low-As aquifers from which drinking water is increasingly drawn in Bangladesh. PMID:21405115

Factors influencing the dissolved iron input by river water to the open ocean

NASA Astrophysics Data System (ADS)

Krachler, R.; Jirsa, F.; Ayromlou, S.

The influence of natural metal chelators on the bio-available iron input to the ocean by river water was studied. Ferrous and ferric ions present as suspended colloidal particles maintaining the semblance of a dissolved load are coagulated and settled as their freshwater carrier is mixed with seawater at the continental boundary. However, we might argue that different iron-binding colloids become sequentially destabilized in meeting progressively increasing salinities. By use of a 59Fe tracer method, the partitioning of the iron load from the suspended and dissolved mobile fraction to storage in the sediments was measured with high accuracy in mixtures of natural river water with artificial sea water. The results show a characteristic sequence of sedimentation. Various colloids of different stability are removed from a water of increasing salinity, such as it is the case in the transition from a river water to the open sea. However, the iron transport capacities of the investigated river waters differed greatly. A mountainous river in the Austrian Alps would add only about 5% of its dissolved Fe load, that is about 2.0 µg L-1 Fe, to coastal waters. A small tributary draining a sphagnum peat-bog, which acts as a source of refractory low-molecular-weight fulvic acids to the river water, would add approximately 20% of its original Fe load, that is up to 480 µg L-1 Fe to the ocean's bio-available iron pool. This points to a natural mechanism of ocean iron fertilization by terrigenous fulvic-iron complexes originating from weathering processes occurring in the soils upstream.

Factors influencing the dissolved iron input by river water to the open ocean

NASA Astrophysics Data System (ADS)

Krachler, R.; Jirsa, F.; Ayromlou, S.

2005-05-01

The influence of natural metal chelators on the bio-available iron input to the ocean by river water was studied. Ferrous and ferric ions present as suspended colloidal particles maintaining the semblance of a dissolved load are coagulated and settled as their freshwater carrier is mixed with seawater at the continental boundary. However, we might argue that different iron-binding colloids become sequentially destabilized in meeting progressively increasing salinities. By use of a 59Fe tracer method, the partitioning of the iron load from the suspended and dissolved mobile fraction to storage in the sediments was measured with high accuracy in mixtures of natural river water with artificial sea water. The results show a characteristic sequence of sedimentation. Various colloids of different stability are removed from a water of increasing salinity, such as it is the case in the transition from a river water to the open sea. However, the iron transport capacities of the investigated river waters differed greatly. A mountainous river in the Austrian Alps would add only about 5% of its dissolved Fe load, that is about 2.0 µg L-1 Fe, to coastal waters. A small tributary draining a sphagnum peat-bog, which acts as a source of refractory low-molecular-weight fulvic acids to the river water, would add approximately 20% of its original Fe load, that is up to 480 µg L-1 Fe to the ocean's bio-available iron pool. This points to a natural mechanism of ocean iron fertilization by terrigenous fulvic-iron complexes originating from weathering processes occurring in the soils upstream.

Temporal geochemical variations in above- and below-drainage coal mine discharge

USGS Publications Warehouse

Burrows, Jill E.; Peters, Stephen C.; Cravotta, Charles A.

2015-01-01

Water quality data collected in 2012 for 10 above- and 14 below-drainage coal mine discharges (CMDs), classified by mining or excavation method, in the anthracite region of Pennsylvania, USA, are compared with data for 1975, 1991, and 1999 to evaluate long-term (37 year) changes in pH, SO42−, and Fe concentrations related to geochemistry, hydrology, and natural attenuation processes. We hypothesized that CMD quality will improve over time because of diminishing quantities of unweathered pyrite, decreased access of O2 to the subsurface after mine closure, decreased rates of acid production, and relatively constant influx of alkalinity from groundwater. Discharges from shafts, slopes, and boreholes, which are vertical or steeply sloping excavations, are classified as below-drainage; these receive groundwater inputs with low dissolved O2, resulting in limited pyrite oxidation, dilution, and gradual improvement of CMD water quality. In contrast, discharges from drifts and tunnels, which are nearly horizontal excavations into hillsides, are classified as above-drainage; these would exhibit less improvement in water quality over time because the rock surfaces continue to be exposed to air, which facilitates sustained pyrite oxidation, acid production, and alkalinity consumption. Nonparametric Wilcoxon matched-pair signed rank tests between 1975 and 2012 samples indicate decreases in Fe and SO42− concentrations were highly significant (p < 0.05) and increases in pH were marginally significant (p < 0.1) for below-drainage discharges. For above-drainage discharges, changes in Fe and SO42−concentrations were not significant, and increases in pH were highly significant between 1975 and 2012. Although a greater proportion of above-drainage discharges were net acidic in 2012 compared to below-drainage discharges, the increase in pH between 1975 and 2012 was greater for above- (median pH increase from 4.4 to 6.0) compared to below- (median pH increase from 5.6 to 6.1) drainage discharges. For cases where O2 is limited, transformation of aqueous FeII species to FeIII may be kinetically limited. In contrast, where O2 is abundant, aqueous Fe concentrations may be limited by FeIIImineral precipitation; thus, trends in Fe may not follow those for SO42−. In either case, when the supply of alkalinity is sufficient to buffer decreased acidity, the pH could increase by a step trend from strongly acidic (3–3.5) to near neutral (6–6.5) values. Modeled equilibrium with respect to FeIII precipitates varies with pH and Fe and SO42−reconcentrations: increasing pH promotes the formation of ferrihydrite, while decreasing concentrations of Fe limit the formation of ferrihydrite, and decreasing Fe and SO42−concentrations limit the precipitation of schwertmannite and favor formation of FeIIIhydroxyl complexes and uncomplexed Fe2+ and Fe3+. The analysis of the long-term geochemical changes in CMDs in the anthracite field and the effect of the hydrologic setting on water quality presented in this paper can help prioritize CMD remediation and facilitate selection and design of the most appropriate treatment systems.

Chemical constituents in the Peedee and Castle Hayne aquifers: Porters Neck area, New Hanover County, North Carolina

USGS Publications Warehouse

Roberts, T.L.; Harris, W.B.

2004-01-01

Concerns about overuse and potential contamination of major aquifers in the southeastern part of North Carolina resulted in the initiation of a subsurface water quality study in February 2001. The focus of this study was to examine variations in nutrients (NO3-, TRP, SO42- Cl-, NH4+) and total dissolved Fe in the Cretaceous Peedee and Tertiary Castle Hayne Limestone aquifers of northeastern New Hanover County. Water samples were collected monthly for one year from sixteen wells located in the Porters Neck area (west of the Intracoastal Waterway and south of Futch Creek) and four springs located on the south side of Futch Creek. Variations in selective nutrient concentrations were measured between and within each aquifer. Concentrations of NH4+ and Fe increased in the Peedee sandstone aquifer during the warmer summer and early fall months. In late summer to early fall, Fe, NO 3-, NH4+, and TRP concentrations in the Castle Hayne Limestone aquifer were significantly higher than in the spring and winter months. Chloride and SO 42- concentrations for the Castle Hayne Limestone aquifer both increased during the warmer months, probably as a result of saltwater intrusion. Factors considered for nutrient and Fe variance include: temperature variation, anaerobic conditions, subsurface stratigraphy/structure, recharge locations, site location and surface fertilization. The shallower Castle Hayne Limestone aquifer showed seasonal variability in the study area, whereas the Peedee sandstone aquifer showed little to no seasonal variability. Increases in NO3- and TRP lagged slightly behind periods of high fertilization and were more prevalent down-dip of a major golf course. Nutrient content and seasonal variation of Futch Creek springs indicated that they originate from the Castle Hayne Limestone aquifer.

Sulfate radical degradation of acetaminophen by novel iron-copper bimetallic oxidation catalyzed by persulfate: Mechanism and degradation pathways

NASA Astrophysics Data System (ADS)

Zhang, Yuanchun; Zhang, Qian; Hong, Junming

2017-11-01

A novel iron coupled copper oxidate (Fe2O3@Cu2O) catalyst was synthesized to activate persulfate (PS) for acetaminophen (APAP) degradation. The catalysts were characterized via field-emission scanning electron microscopy and energy-dispersive X-ray spectrometry. The effects of the catalyst, PS concentration, catalyst dosage, initial pH, dissolved oxygen were analyzed for treatment optimization. Results indicated that Fe2O3@Cu2O achieved higher efficiency in APAP degradation than Fe2O3/PS and Cu2O/PS systems. The optimal removal efficiency of APAP (90%) was achieved within 40 min with 0.6 g/L PS and 0.3 g/L catalyst. To clarify the mechanism for APAP degradation, intermediates were analyzed with gas chromatography-mass spectrometry. Three possible degradation pathways were identified. During reaction, Cu(I) was found to react with Fe(III) to generate Fe(II), which is the most active phase for PS activation. Through the use of methanol and tert-butyl alcohol (TBA) as radical trappers, SO4rad - was identified as the main radical species that is generated during oxidation.

Trivalent Actinide Uptake by Iron (Hydr)oxides.

PubMed

Finck, Nicolas; Nedel, Sorin; Dideriksen, Knud; Schlegel, Michel L

2016-10-04

The retention of Am(III) by coprecipitation with or adsorption onto preformed magnetite was investigated by X-ray diffraction (XRD), solution chemistry, and X-ray absorption spectroscopy (XAS). In the coprecipitation experiment, XAS data indicated the presence of seven O atoms at 2.44(1) Å, and can be explained by an Am incorporation at Fe structural sites at the magnetite surface. Next-nearest Fe were detected at distances suggesting that Am and Fe polyhedra share corners in geometries ranging from bent to close to linear Am-O-Fe bonds. After aging for two years, the coordination number and the distance to the first O shell significantly decreased, and atomic shells were detected at higher distances. These data suggest a structural reorganization and an increase in structural order around sorbed Am. Upon contact with preformed Fe 3 O 4 , Am(III) forms surface complexes with cosorbed Fe at the surface of magnetite, a possible consequence of the high concentration of dissolved Fe. In a separate experiment, chloride green rust (GR) was synthesized in the presence of Am(III), and subsequently converted to Fe(OH) 2 (s) intermixed with magnetite. XAS data indicated that the actinide is successively located first at octahedral brucite-like sites in the GR precursor, then in Fe(OH) 2 (s), an environment markedly distinct from that of Am(III) in Fe 3 O 4 . The findings indicate that the magnetite formation pathway dictates the magnitude of Am(III) incorporation within this solid.

Responses of phytoplankton community to the input of different aerosols in the East China Sea

NASA Astrophysics Data System (ADS)

Meng, X.; Chen, Y.; Wang, B.; Ma, Q. W.; Wang, F. J.

2016-07-01

Atmospheric deposition can affect marine phytoplankton by supplying macronutrients and trace elements. We conducted mesocosm experiments by adding aerosols with different composition (dominated by mineral dust, biomass burning and high Cu, and secondary aerosol, respectively) to the surface seawater of the East China Sea. Chlorophyll a concentrations were found to be the highest and lowest after adding aerosols containing the highest Fe and dissolved inorganic nitrogen (DIN), respectively. The relative abundance of Haptophyceae increased significantly after adding mineral dust, whereas diatom, Dinophyceae and Cryptophyceae reached the maximum accompanied with the highest DIN. Our results suggest that Fe may be more important than DIN in promoting primary productivity in the sampled seawater. The input of mineral dust and anthropogenic aerosols may result in distinct changes of phytoplankton community structure.

The origin of high sulfate concentrations in a coastal plain aquifer, Long Island, New York

USGS Publications Warehouse

Brown, C.J.; Schoonen, M.A.A.

2004-01-01

Ion-exchange batch experiments were run on Cretaceous (Magothy aquifer) clay cores from a nearshore borehole and an inland borehole on Long Island, NY, to determine the origin of high SO42- concentrations in ground water. Desorption batch tests indicate that the amounts of SO 42- released from the core samples are much greater (980-4700 ??g/g of sediment) than the concentrations in ground-water samples. The locally high SO42- concentrations in pore water extracted from cores are consistent with the overall increase in SO 42- concentrations in ground water along Magothy flow paths. Results of the sorption batch tests indicate that SO42- sorption onto clay is small but significant (40-120 ??g/g of sediment) in the low-pH (<5) pore water of clays, and a significant part of the SO42- in Magothy pore water may result from the oxidation of FeS2 by dissolved Fe(III). The acidic conditions that result from FeS2 oxidation in acidic pore water should result in greater sorption of SO42- and other anions onto protonated surfaces than in neutral-pH pore water. Comparison of the amounts of Cl- released from a clay core sample in desorption batch tests (4 ??g/g of sediment) with the amounts of Cl- sorbed to the same clay in sorption tests (3.7-5 ??g/g) indicates that the high concentrations of Cl- in pore water did not originate from connate seawater but were desorbed from sediment that was previously in contact with seawater. Furthermore, a hypothetical seawater transgression in the past is consistent with the observed pattern of sorbed cation complexes in the Magothy cores and could be a significant source of high SO42- concentrations in Magothy ground water.

Atmospheric Processing of Volcanic Glass: Effects on Iron Solubility and Redox Speciation.

PubMed

Maters, Elena C; Delmelle, Pierre; Bonneville, Steeve

2016-05-17

Volcanic ash from explosive eruptions can provide iron (Fe) to oceanic regions where this micronutrient limits primary production. Controls on the soluble Fe fraction in ash remain poorly understood but Fe solubility is likely influenced during atmospheric transport by condensation-evaporation cycles which induce large pH fluctuations. Using glass powder as surrogate for ash, we experimentally simulate its atmospheric processing via cycles of pH 2 and 5 exposure. Glass fractional Fe solubility (maximum 0.4%) is governed by the pH 2 exposure duration rather than by the pH fluctuations, however; pH 5 exposure induces precipitation of Fe-bearing nanoparticles which (re)dissolve at pH 2. Glass leaching/dissolution release Fe(II) and Fe(III) which are differentially affected by changes in pH; the average dissolved Fe(II)/Fetot ratio is ∼0.09 at pH 2 versus ∼0.18 at pH 5. Iron release at pH 2 from glass with a relatively high bulk Fe(II)/Fetot ratio (0.5), limited aqueous Fe(II) oxidation at pH 5, and possibly glass-mediated aqueous Fe(III) reduction may render atmospherically processed ash a significant source of Fe(II) for phytoplankton. By providing new insight into the form(s) of Fe associated with ash as wet aerosol versus cloud droplet, we improve knowledge of atmospheric controls on volcanogenic Fe delivery to the ocean.

Arsenic release by indigenous bacteria Bacillus cereus from aquifer sediments at Datong Basin, northern China

NASA Astrophysics Data System (ADS)

Xie, Zuoming; Wang, Yanxin; Duan, Mengyu; Xie, Xianjun; Su, Chunli

2011-03-01

Endemic arsenic poisoning due to long-term drinking of high arsenic groundwater has been reported in Datong Basin, northern China. To investigate the effects of microbial activities on arsenic mobilization in contaminated aquifers, Bacillus cereus ( B. cereus) isolated from high arsenic aquifer sediments of the basin was used in our microcosm experiments. The arsenic concentration in the treatment with both bacteria and sodium citrate or glucose had a rapid increase in the first 18 d, and then, it declined. Supplemented with bacteria only, the concentration could increase on the second day. By contrast, the arsenic concentration in the treatment supplemented with sodium citrate or glucose was kept very low. These results indicate that bacterial activities promoted the release of arsenic in the sediments. Bacterial activities also influenced other geochemical parameters of the aqueous phase, such as pH, Eh, and the concentrations of dissolved Fe, Mn, and Al that are important controls on arsenic release. The removal of Fe, Mn, and Al from sediment samples was observed with the presence of B. cereus. The effects of microbial activities on Fe, Mn, and Al release were nearly the same as those on As mobilization. The pH values of the treatments inoculated with bacteria were lower than those without bacteria, still at alkaline levels. With the decrease of Eh values in treatments inoculated with bacteria, the microcosms became more reducing and are thus favorable for arsenic release.

Dissolved metals and associated constituents in abandoned coal-mine discharges, Pennsylvania, USA. Part 1: Constituent quantities and correlations

USGS Publications Warehouse

Cravotta, C.A.

2008-01-01

Complete hydrochemical data are rarely reported for coal-mine discharges (CMD). This report summarizes major and trace-element concentrations and loadings for CMD at 140 abandoned mines in the Anthracite and Bituminous Coalfields of Pennsylvania. Clean-sampling and low-level analytical methods were used in 1999 to collect data that could be useful to determine potential environmental effects, remediation strategies, and quantities of valuable constituents. A subset of 10 sites was resampled in 2003 to analyze both the CMD and associated ochreous precipitates; the hydrochemical data were similar in 2003 and 1999. In 1999, the flow at the 140 CMD sites ranged from 0.028 to 2210 L s-1, with a median of 18.4 L s-1. The pH ranged from 2.7 to 7.3; concentrations (range in mg/L) of dissolved (0.45-??m pore-size filter) SO4 (34-2000), Fe (0.046-512), Mn (0.019-74), and Al (0.007-108) varied widely. Predominant metalloid elements were Si (2.7-31.3 mg L-1), B ( C > P = N = Se) were not elevated in the CMD samples compared to average river water or seawater. Compared to seawater, the CMD samples also were poor in halogens (Cl > Br > I > F), alkalies (Na > K > Li > Rb > Cs), most alkaline earths (Ca > Mg > Sr), and most metalloids but were enriched by two to four orders of magnitude with Fe, Al, Mn, Co, Be, Sc, Y and the lanthanide rare-earth elements, and one order of magnitude with Ni and Zn. The ochre samples collected at a subset of 10 sites in 2003 were dominantly goethite with minor ferrihydrite or lepidocrocite. None of the samples for this subset contained schwertmannite or was Al rich, but most contained minor aluminosilicate detritus. Compared to concentrations in global average shale, the ochres were rich in Fe, Ag, As and Au, but were poor in most other metals and rare earths. The ochres were not enriched compared to commercial ore deposits mined for Au or other valuable metals. Although similar to commercial Fe ores in composition, the ochres are dispersed and present in relatively small quantities at most sites. Nevertheless, the ochres could be valuable for use as pigment.

Redox-induced mobilization of copper, selenium, and zinc in deltaic soils originating from Mississippi (U.S.A.) and Nile (Egypt) River Deltas: A better understanding of biogeochemical processes for safe environmental management.

PubMed

Shaheen, Sabry M; Frohne, Tina; White, John R; DeLaune, Ron D; Rinklebe, Jörg

2017-01-15

Studies about the mobilization of potentially toxic elements (PTEs) in deltaic soils can be challenging, provide critical information on assessing the potential risk and fate of these elements and for sustainable management of these soils. The impact of redox potential (E H ), pH, iron (Fe), manganese (Mn), sulfate (SO 4 2- ), chloride (Cl - ), aliphatic dissolved organic carbon (DOC), and aromatic dissolved organic carbon (DAC) on the mobilization of copper (Cu), selenium (Se), and zinc (Zn) was studied in two soils collected from the Nile and Mississippi Rivers deltaic plains focused on increasing our understanding of the fate of these toxic elements. Soils were exposed to a range of redox conditions stepwise from reducing to oxidizing soil conditions using an automated biogeochemical microcosm apparatus. Concentrations of DOC and Fe were high under reducing conditions as compared to oxidizing conditions in both soils. The proportion of DAC in relation to DOC in solution (aromaticity) was high in the Nile Delta soil (NDS) and low in the Mississippi Delta soil (MDS) under oxidizing conditions. Mobilization of Cu was low under reducing conditions in both soils which was likely caused by sulfide precipitation and as a result of reduction of Cu 2+ to Cu 1+ . Mobilization of Se was high under low E H in both soils. Release of Se was positively correlated with DOC, Fe, Mn, and SO 4 2- in the NDS, and with Fe in the MDS. Mobilization of Zn showed negative correlations with E H and pH in the NDS while these correlations were non-significant in the MDS. The release dynamics of dissolved Zn could be governed mainly by the chemistry of Fe and Mn in the NDS and by the chemistry of Mn in the MDS. Our findings suggest that a release of Se and Zn occurs under anaerobic conditions, while aerobic conditions favor the release of Cu in both soils. In conclusion, the release of Cu, Se, and Zn under different reducing and oxidizing conditions in deltaic wetland soils should be taken into account due to increased mobilization and the potential environmental risks associated with food security in utilizing these soils for flooded agricultural and fisheries systems. Copyright © 2016 Elsevier Ltd. All rights reserved.

Catchment-fed cyanobacterial blooms in brownified temperate lakes

NASA Astrophysics Data System (ADS)

Senar, O.; Creed, I. F.

2017-12-01

One of the most significant impacts of global atmospheric change is the alteration of hydrological regimes and the associated disruption of hydrological connectivity within watersheds. We show how changes in the frequency, magnitude, and duration of hydrological connectivity and disconnectivity is compromising the capacity of forest soils to store organic carbon, and increasing its export to both aquatic and atmospheric systems. Increases in dissolved organic matter (DOM) loads from forested landscapes to aquatic systems and the shift of the DOM pool to a more refractory mixture of organic compounds, a process known as brownification, alters the physical and chemical characteristics of lake environments. Furthermore, by characterizing the stages of brownification (from low to high concentrations of refractory DOM), we show a shift in the limiting factors for phytoplankton growth from macronutrients (nitrogen -N- and phosphorus -P) to micronutrients (iron -Fe) and light availability. This shift is driven by the low concentrations of DOM supplying N and P in early stages of brownification, to the strong Fe-binding capacity of refractory DOM in brownified lakes. As lakes undergo brownification, cyanobacteria adapted to scavenge Fe from DOM-Fe complexes have a competitive advantage leading to the formation of cyanobacterial blooms. Our findings provide evidence that brownification is a driving force leading to cyanobacterial blooms in lakes on forested landscapes, with expected cascading consequences to lake food webs.

Determining the Pollution Parameters of Degirmendere Stream (Trabzon, NE TURKEY)

NASA Astrophysics Data System (ADS)

Sunnetci, M. O.; Hatipoglu, E.; Firat Ersoy, A.; Gultekin, F.

2013-12-01

The pollution parameters of Degirmendere Stream (Trabzon, TURKEY) are determined in this study. The study area is located between Maçka, 26 km to the south of Trabzon city, and the Black Sea. The area consists of Late Cretaceous volcano-sedimentary rocks, dacite, and basalt, overlain by Eocene volcanic rocks. Quaternary alluvium overlay all geological units following Degirmendere Stream bed. In-situ physical parameter measurements, anion-cation analysis, and heavy and pollutant element analysis on water samples were carried out for four months at four different locations on the stream. The stream's water temperature values were between 4.7 and 9.7oC, pH values were between 6.01 and 7.98, dissolved oxygen (DO) values were between 7.03 and 12.38 mg/l, electrical conductivity (EC) values were between 86 and 254 μS/cm. According to the Piper diagram, the stream water is classified as Ca-HCO3 type water. In the Schoeller diagram, the lines combining mek/l values of the ions in stream water are parallel. Al concentration in the stream water varied from 0.06 to 0.22 mg/l, Mn concentration varied from 0.1 to 0.36 mg/l, and Fe concentration varied from 0.01 to 0.12 mg/l. The stream water is classified as first class in point of temperature, pH, DO, total dissolved solids (TDS), NO3-, P, Pb, Fe, and Al; first and second class in point of NH4+; second class in point of Cu; and third class in point of NO2-, according to the Water Pollution Control Regulation of the Turkish Republic's Criteria for Inland Surface Water Classification. Results indicate waters of the Degirmendere Stream is very good-good for irrigation use according to the Wilcox diagram.

Arsenic removal from contaminated brackish sea water by sorption onto Al hydroxides and Fe phases mobilized by land-use.

PubMed

Yu, Changxun; Peltola, Pasi; Nystrand, Miriam I; Virtasalo, Joonas J; Österholm, Peter; Ojala, Antti E K; Hogmalm, Johan K; Åström, Mats E

2016-01-15

This study examines the spatial and temporal distribution patterns of arsenic (As) in solid and aqueous materials along the mixing zone of an estuary, located in the south-eastern part of the Bothnian Bay and fed by a creek running through an acid sulfate (AS) soil landscape. The concentrations of As in solution form (<1 kDa) increase steadily from the creek mouth to the outer estuary, suggesting that inflowing seawater, rather than AS soil, is the major As source in the estuary. In sediments at the outer estuary, As was accumulated and diagenetically cycled in the surficial layers, as throughout much of the Bothnian Bay. In contrast, in sediments in the inner estuary, As concentrations and accumulation rates showed systematical peaks at greater depths. These peaks were overall consistent with the temporal trend of past As discharges from the Rönnskär smelter and the accompanied As concentrations in past sea-water of the Bothnian Bay, pointing to a connection between the historical smelter activities and the sediment-bound As in the inner estuary. However, the concentrations and accumulation rates of As peaked at depths where the smelter activities had already declined, but a large increase in the deposition of Al hydroxides and Fe phases occurred in response to intensified land-use in the mid 1960's and early 1970's. This correspondence suggests that, apart from the inflowing As-contaminated seawater, capture by Al hydroxides, Fe hydroxides and Fe-organic complexes is another important factor for As deposition in the inner estuary. After accumulating in the sediment, the solid-phase As was partly remobilized, as reflected by increased pore-water As concentrations, a process favored by As(V) reduction and high concentrations of dissolved organic matter. Copyright © 2015 Elsevier B.V. All rights reserved.

In situ removal of dissolved and suspended contaminants from a eutrophic pond using hybrid sand-filter.

PubMed

Vijayaraghavan, K; Joshi, Umid Man; Ping, Han; Reuben, Sheela; Burger, David F

2014-01-01

In this study, in situ hybrid sand filters were designed to remove dissolved and suspended contaminants from eutrophic pond. Currently, there are no attempts made to eradicate dissolved as well as suspended contaminants from eutrophic water system in a single step. Monitoring studies revealed that examined pond contain high chlorophyll-a content (101.8 μg L(-1)), turbidity (39.5 NTU) and total dissolved solids concentration (0.04 g L(-1)). Samples were further exposed to extensive water quality analysis, which include examining physicochemical parameters (pH, conductivity, total dissolved solids, salinity, turbidity and chlorophyll-a), metals (Na, K, Ca, Mg, Al, Fe, Cu, Cd, Pb, Zn, Cr, and Ni) and anions (NO3, NO2, PO4, SO4, Cl, F and Br). To tackle pollutants, filtration system was designed to comprise of several components including fine sand, coarse sand/sorbent mix and gravel from top to bottom loaded in fiberglass tanks. All the filters (activated carbon, Sargassum and zeolite) completely removed algal biomass and showed potential to decrease pH during entire operational period of 20 h at 120 L h(-1). To examine the efficiency of filters in adverse conditions, the pond water was spiked with heavy metals (Cu, Cd, Pb, Zn, Cr, and Ni). Of the different filter systems, Sargassum-loaded filter performed exceedingly well with concentrations of heavy metals never exceeded the Environmental protection agency regulations for freshwater limits during total operational period. The total uptake capacities at the end of the fifth event were 24.9, 20.5, 0.58, 5.2, 0.091 and 2.8 mg/kg for Cr, Ni, Cu, Zn, Cd and Pb, respectively.

Predicting organic matter, nitrogen, and phosphorus concentrations in runoff from peat extraction sites using partial least squares regression

NASA Astrophysics Data System (ADS)

Tuukkanen, T.; Marttila, H.; Kløve, B.

2017-07-01

Organic matter and nutrient export from drained peatlands is affected by complex hydrological and biogeochemical interactions. Here partial least squares regression (PLSR) was used to relate various soil and catchment characteristics to variations in chemical oxygen demand (COD), total nitrogen (TN), and total phosphorus (TP) concentrations in runoff. Peat core samples and water quality data were collected from 15 peat extraction sites in Finland. PLSR models constructed by cross-validation and variable selection routines predicted 92, 88, and 95% of the variation in mean COD, TN, and TP concentration in runoff, respectively. The results showed that variations in COD were mainly related to net production (temperature and water-extractable dissolved organic carbon (DOC)), hydrology (topographical relief), and solubility of dissolved organic matter (peat sulfur (S) and calcium (Ca) concentrations). Negative correlations for peat S and runoff COD indicated that acidity from oxidation of organic S stored in peat may be an important mechanism suppressing organic matter leaching. Moreover, runoff COD was associated with peat aluminum (Al), P, and sodium (Na) concentrations. Hydrological controls on TN and COD were similar (i.e., related to topography), whereas degree of humification, bulk density, and water-extractable COD and Al provided additional explanations for TN concentration. Variations in runoff TP concentration were attributed to erosion of particulate P, as indicated by a positive correlation with suspended sediment concentration (SSC), and factors associated with metal-humic complexation and P adsorption (peat Al, water-extractable P, and water-extractable iron (Fe)).

Dynamics of Chromium(VI) Removal from Drinking Water by Iron Electrocoagulation.

PubMed

Pan, Chao; Troyer, Lyndsay D; Catalano, Jeffrey G; Giammar, Daniel E

2016-12-20

The potential for new U.S. regulations for Cr(VI) in drinking water have spurred strong interests in improving technologies for Cr(VI) removal. This study examined iron electrocoagulation for Cr(VI) removal at conditions directly relevant to drinking water treatment. Cr(VI) is chemically reduced to less soluble Cr(III) species by the Fe(II) produced from an iron anode, and XANES spectra indicate that the Cr is entirely Cr(III) in solid-phases produced in electrocoagulation. The dynamics of Cr(VI) removal in electrocoagulation at pH 6 and pH 8 at both oxic and anoxic conditions can be described by a new model that incorporates Fe(II) release from the anode and heterogeneous and homogeneous reduction of Cr(VI) by Fe(II). Heterogeneous Cr(VI) reduction by adsorbed Fe(II) was critical to interpreting Cr(VI) removal at pH 6, and the Fe- and Cr-containing EC product was found to catalyze the redox reaction. Dissolved oxygen (DO) did not observably inhibit Cr(VI) removal because Fe(II) reacts with DO more slowly than it does with Cr(VI), and Cr(VI) removal was faster at higher pH. Even in the presence of common groundwater solutes, iron electrocoagulation lowered Cr(VI) concentrations to levels well below California's 10 μg/L.

Experimental modeling of thaw lake water evolution in discontinuous permafrost zone: Role of peat, lichen leaching and ground fire.

PubMed

Manasypov, Rinat M; Shirokova, Liudmila S; Pokrovsky, Oleg S

2017-02-15

Thaw of frozen peat in discontinuous permafrost zone produces a significant number of thermokarst lakes, which are known to contribute to Green House Gases (GHG) emission in the atmosphere. In palsa peatland of western Siberia, the thermokarst lake formation includes soil subsidences, lichen submergence and peat abrasion, leading to lateral spreading of the lake border, often intensified by ground fires. Mesocosm experiments were conducted during 3weeks on two thermokarst lake waters interacting in 30-L tanks with surface horizon of peat, the dominant ground vegetation (lichen Cladonia sp.) and the ash produced by lichen burning at 450°C. The obtained results allowed a better understanding of physico-chemical factors controlling the enrichment of thermokarst lake water in organic carbon and metals, and evaluating CO 2 sequestration/emission potential. The changes of dissolved organic carbon (DOC) and dissolved inorganic carbon (DIC), major element and divalent metal concentration in response to peat and lichen biomass addition were less than a factor of 2 over full duration of the experiment. Iron (Fe) concentration in the lake water decreased by a factor of 2 to 3 after the addition of peat and lichen biomass. The concentration of low-soluble trivalent and tetravalent hydrolysates decreased by ca. 30 to 50%, presumably due to their co-precipitation with Fe hydroxide. The dissolved carbon dioxide (CO 2 ) in tank with lichen increased by a factor of 5.5±0.5, likely due to respiration of algal component in closed environment. Strong enrichment of the lake water in DIC, P, K, Ca, Mg, Si, Al, Ti, Mn, Mo, Rb, As, Sb and U upon the ash addition persisted over full duration of experiments and was significant (p<0.0001) compared to peat and lichen biomass treatments. These elements may serve as indicators of ground fire impact on thermokarst lake water's chemistry. The overall effect of ash leaching on aquatic ecosystems after ground fire of frozen Siberian peatland is predicted to be much stronger than that currently recognized for non-permafrost regions. Copyright © 2016 Elsevier B.V. All rights reserved.

Sustaining 1,2-Dichloroethane Degradation in Nanoscale Zero-Valent Iron induced Fenton system by using Sequential H2O2 Addition at Natural pH

NASA Astrophysics Data System (ADS)

Phenrat, T.; Le, T. S. T.

2017-12-01

1,2-Dichloroethane (1,2-DCA) is a prevalent subsurface contaminant found in groundwater and soil around the world. Nanoscale zero-valent iron (NZVI) is a promising in situ remediation agent for chlorinated organics. Nevertheless, 1,2-DCA is recalcitrant to reductive dechlorination using NZVI. Chemical oxidation using Fenton's reaction with conventional Fe2+ is a valid option for 1,2-DCA remediation with a major technical challenge, i.e. aquifer acidification is needed to maintain Fe2+ for catalytic reaction. In this work, NZVI Fenton's process at neutral pH was applied to degrade 1,2-DCA at high concentration (2,000 mg/L) representing dissolved 1,2-DCA concentration close to non-aqueous phase liquid source zone. Instead of using acidification to maintain dissolved Fe2+ concentration, NZVI Fenton's process is self-catalytic based on oxidative dissolution of NZVI in the present of H2O2. Interfacial H+ is produced at NZVI surface to provide appropriate local pH which continuously releases Fe2+ for Fenton's reaction. Approximately, 87% of 1,2-DCA was degraded at neutral pH with the pseudo first-order rate constant of 0.98 hour-1 using 10 g/L of NZVI and 200 mM of H2O2. However, the reaction was prohibited quickly within 3 hours presumably due to the rapid depletion of H2O2. The application of sequential H2O2 addition provided a better approach to prevent rapid inhibition via controlling the H2O2 concentration in the system to be sufficient but not excess, thus resulting in the higher degradation efficiency (the pseudo first-order rate constant of 0.49 hour-1 and 99 % degradation in 8 hours). Using NZVI with sequential H2O2 addition was also successful in degrading 1,2-DCA sorbed on to soil, yielding 99% removal of 1,2-DCA within 16 hours at the rate constant of 0.23 hour-1, around two times slower than in the system without soil presumably due to rate-limited 1,2-DCA desorption from soil. Mechanistic understanding of how sequential addition of H2O2, in comparison to the simultaneous H2O2 addition, can sustain oxidative degradation of 1,2-DCA was also proposed in addition to the investigation of NZVI reusability in three consecutive 1, 2-DCA degradation cycles.

Source and fate of inorganic solutes in the Gibbon River, Yellowstone National Park, Wyoming, USA. II. Trace element chemistry

USGS Publications Warehouse

McCleskey, R. Blaine; Nordstrom, D. Kirk; Susong, David D.; Ball, James W.; Taylor, Howard E.

2010-01-01

The Gibbon River in Yellowstone National Park receives inflows from several geothermal areas, and consequently the concentrations of many trace elements are elevated compared to rivers in non-geothermal watersheds. Water samples and discharge measurements were obtained from the Gibbon River and its major tributaries near Norris Geyser Basin under the low-flow conditions of September 2006 allowing for the identification of solute sources and their downstream fate. Norris Geyser Basin, and in particular Tantalus Creek, is the largest source of many trace elements (Al, As, B, Ba, Br, Cs, Hg, Li, Sb, Tl, W, and REEs) to the Gibbon River. The Chocolate Pots area is a major source of Fe and Mn, and the lower Gibbon River near Terrace Spring is the major source of Be and Mo. Some of the elevated trace elements are aquatic health concerns (As, Sb, and Hg) and knowing their fate is important. Most solutes in the Gibbon River, including As and Sb, behave conservatively or are minimally attenuated over 29 km of fluvial transport. Some small attenuation of Al, Fe, Hg, and REEs occurs but primarily there is a transformation from the dissolved state to suspended particles, with most of these elements still being transported to the Madison River. Dissolved Hg and REEs loads decrease where the particulate Fe increases, suggesting sorption onto suspended particulate material. Attenuation from the water column is substantial for Mn, with little formation of Mn as suspended particulates.

Carbon, nutrient and trace metal cycling in sandy sediments: A comparison of high-energy beaches and backbarrier tidal flats

NASA Astrophysics Data System (ADS)

Reckhardt, Anja; Beck, Melanie; Seidel, Michael; Riedel, Thomas; Wehrmann, Achim; Bartholomä, Alexander; Schnetger, Bernhard; Dittmar, Thorsten; Brumsack, Hans-Jürgen

2015-06-01

In order to evaluate the importance of coastal sandy sediments and their contribution to carbon, nutrient and metal cycling we investigated two beach sites on Spiekeroog Island, southern North Sea, Germany, and a tidal flat margin, located in Spiekeroog's backbarrier area. We also analyzed seawater and fresh groundwater on Spiekeroog Island, to better define endmember concentrations, which influence our study sites. Intertidal sandy flats and beaches are characterized by pore water advection. Seawater enters the sediment during flood and pore water drains out during ebb and at low tide. This pore water circulation leads to continuous supply of fresh organic substrate to the sediments. Remineralization products of microbial degradation processes, i.e. nutrients, and dissolved trace metals from the reduction of particulate metal oxides, are enriched in the pore water compared to open seawater concentrations. The spatial distribution of dissolved organic carbon (DOC), nutrients (PO43-, NO3-, NO2-, NH4+, Si(OH)4 and total alkalinity), trace metals (dissolved Fe and Mn) as well as sulfate suggests that the exposed beach sites are subject to relatively fast pore water advection, which leads to organic matter and oxygen replenishment. Frequent pore water exchange further leads to comparatively low nutrient concentrations. Sulfate reduction does not appear to play a major role during organic matter degradation. High nitrate concentrations indicate that redox conditions are oxic within the duneward freshwater influenced section, while ammonification, denitrification, manganese and iron reduction seem to prevail in the ammonium-dominated seawater circulation zone. In contrast, the sheltered tidal flat margin site exhibits a different sedimentology (coarser beach sands versus finer tidal flat sands) and nutrients, dissolved manganese and DOC accumulate in the pore water. Ammonium is the dominant pore water nitrogen species and intense sulfate reduction leads to the formation of sulfide, which precipitates dissolved iron as iron sulfide. These findings are due to slower advective pore water exchange in the tidal flat sediments. This study illustrates how different energy regimes affect biogeochemical cycling in intertidal permeable sediments.

The lacustrine carbon cycle as illuminated by the waters and sediments of two hydrologically distinct headwater lakes in North-Central Minnesota, U.S.A

USGS Publications Warehouse

Dean, W.E.; Schwalb, A.

2002-01-01

The accumulation rates of CaCO3 and organic carbon (OC) in lake sediments are delicately balanced between production in the epilimnion and destruction in the hypolimnion. The cycling of these two forms of carbon makes a "carbon pump" that greatly affects the biogeochemical cycles of other elements. To further understand these biogeochemical dynamics, the lakes, streams, and wetlands of the Shingobee River headwater area of north-central Minnesota have been subjected to intensive hydrologic and biogeochemical studies. Williams Lake, situated close to the highest point in the regional flow system, is hydrologically closed, with no surface inlet or outlet, and ground water and precipitation as the only sources of water. Shingobee Lake, situated at the lowest point in the regional flow system, has the Shingobee River as an inlet and outlet. The surface waters of both lakes are oversaturated, and the bottom waters undersaturated, with respect to CaCO3 during the summer. The small amount of CaCO3 that is precipitated in the epilimnion of Williams Lake during the summer is dissolved in the undersaturated hypolimnion and sediments with the result that no CaCO3 is incorporated into the profundal surface sediments. Because of the high phytoplankton productivity of Shingobee Lake, sufficient CaCO3 is produced in the epilimnion that large amounts survive the corrosive hypolimnion and sediments, and an average of 46 wt. % accumulates in surface sediments. Another consequence of higher phytoplankton productivity in Shingobee Lake is that the hypolimnion becomes oxygen deficient within a month after overturn in both the spring and fall. Because of reducing conditions that develop in the hypolimnion of Shingobee Lake, high concentrations of dissolved Fe and Mn accumulate there during summer stratification. Precipitation of Fe and Mn oxyhydroxides during periods of fall and spring overturn results in high concentrations of Fe and Mn in surface sediments. In Williams Lake, high concentrations of Fe and Mn do not build up in the hypolimnion. The concentration of CaCO3 is about 80 wt. % in lower Holocene sediments of both lakes. The lower Holocene sediments in both lakes also contain high concentrations of Fe and Mn, and the lower Holocene sediments of Shingobee are laminated. The waters of both lakes had identical values of ??13C and ??18O during the early Holocene, but the waters of Williams Lake "evolved" during the early Holocene, increasing about 10??? in both ??13C and ??18O. Deposits of lacustrine marl occur as much as seven meters above the present elevation of Williams Lake, the highest of the two lakes. Taken together, these observations suggest that the lakes were once connected to form a larger lake called Lake Willobee with a hypolimnion that was anoxic, at least seasonally.

Chemical transformations during aging of zerovalent iron nanoparticles in the presence of common groundwater dissolved constituents.

PubMed

Reinsch, Brian C; Forsberg, Brady; Penn, R Lee; Kim, Christopher S; Lowry, Gregory V

2010-05-01

Nanoscale zerovalent iron (NZVI) that was aged in simulated groundwater was evaluated for alterations in composition and speciation over 6 months to understand the possible transformations NZVI could undergo in natural waters. NZVI was exposed to 10 mN of various common groundwater anions (Cl(-), NO(3)(-), SO(4)(2-), HPO(4)(2-), and HCO(3)(-)) or to dissolved oxygen (saturated, approximately 9 mg/L). Fresh and exposed NZVI samples, along with Fe-oxide model compounds, were then analyzed using synchrotron radiation X-ray absorption spectroscopy (XAS) to yield both relative oxidation state, using the X-ray absorption near edge structure (XANES), and quantitative speciation information regarding the types and proportions of mineral species present, from analysis of the extended X-ray absorption fine structure (EXAFS). Over 1 month of aging the dissolved anions inhibited the oxidation of the NZVI to varying degrees. Aging for 6 months, however, resulted in average oxidation states that were similar to each other regardless of the anion used, except for nitrate. Nitrate passivated the NZVI surface such that even after 6 months of aging the particles retained nearly the same mineral and Fe(0) content as fresh NZVI. Linear least-squares combination fitting (LCF) of the EXAFS spectra for 1 month-aged samples indicated that the oxidized particles remain predominantly a binary phase system containing Fe(0) and Fe(3)O(4), while the 6 month aged samples contained additional mineral phases such as vivianite (Fe(3)(PO(4))(2).8H(2)O) and iron sulfate species, possibly schwertmannite (Fe(3+)(16)O(16)(OH,SO(4))(12-13).10-12H(2)O). The presence of these additional mineral species was confirmed using synchrotron-based X-ray diffraction (XRD). NZVI exposed to water saturated with dissolved oxygen showed a rapid (<24 h) loss of Fe(0) and evolved both magnetite and maghemite (gamma-Fe(2)O(3)) within the oxide layer. These findings have implications toward the eventual fate, transport, and toxicity of NZVI used for groundwater remediation.

Investigating vibrational anharmonic couplings in cyanide-bridged transition metal mixed valence complexes using two-dimensional infrared spectroscopy

DOE Office of Scientific and Technical Information (OSTI.GOV)

Slenkamp, Karla M.; Lynch, Michael S.; Van Kuiken, Benjamin E.

2014-02-28

Using polarization-selective two-dimensional infrared (2D IR) spectroscopy, we measure anharmonic couplings and angles between the transition dipole moments of the four cyanide stretching (ν{sub CN}) vibrations found in [(NH{sub 3}){sub 5}Ru{sup III}NCFe{sup II}(CN){sub 5}]{sup −} (FeRu) dissolved in D{sub 2}O and formamide and [(NC){sub 5}Fe{sup II}CNPt{sup IV}(NH{sub 3}){sub 4}NCFe{sup II}(CN){sub 5}]{sup 4−} (FePtFe) dissolved in D{sub 2}O. These cyanide-bridged transition metal complexes serve as model systems for studying the role of high frequency vibrational modes in ultrafast photoinduced charge transfer reactions. Here, we focus on the spectroscopy of the ν{sub CN} modes in the electronic ground state. The FTIR spectramore » of the ν{sub CN} modes of the bimetallic and trimetallic systems are strikingly different in terms of frequencies, amplitudes, and lineshapes. The experimental 2D IR spectra of FeRu and FePtFe and their fits reveal a set of weakly coupled anharmonic ν{sub CN} modes. The vibrational mode anharmonicities of the individual ν{sub CN} modes range from 14 to 28 cm{sup −1}. The mixed-mode anharmonicities range from 2 to 14 cm{sup −1}. In general, the bridging ν{sub CN} mode is most weakly coupled to the radial ν{sub CN} mode, which involves the terminal CN ligands. Measurement of the relative transition dipole moments of the four ν{sub CN} modes reveal that the FeRu molecule is almost linear in solution when dissolved in formamide, but it assumes a bent geometry when dissolved in D{sub 2}O. The ν{sub CN} modes are modelled as bilinearly coupled anharmonic oscillators with an average coupling constant of 6 cm{sup −1}. This study elucidates the role of the solvent in modulating the molecular geometry and the anharmonic vibrational couplings between the ν{sub CN} modes in cyanide-bridged transition metal mixed valence complexes.« less

Reactive transport modeling to study changes in water chemistry induced by CO2 injection at the Frio-I Brine Pilot

USGS Publications Warehouse

Xu, T.; Kharaka, Y.K.; Doughty, C.; Freifeld, B.M.; Daley, T.M.

2010-01-01

To demonstrate the potential for geologic storage of CO2 in saline aquifers, the Frio-I Brine Pilot was conducted, during which 1600 tons of CO2 were injected into a high-permeability sandstone and the resulting subsurface plume of CO2 was monitored using a variety of hydrogeological, geophysical, and geochemical techniques. Fluid samples were obtained before CO2 injection for baseline geochemical characterization, during the CO2 injection to track its breakthrough at a nearby observation well, and after injection to investigate changes in fluid composition and potential leakage into an overlying zone. Following CO2 breakthrough at the observation well, brine samples showed sharp drops in pH, pronounced increases in HCO3- and aqueous Fe, and significant shifts in the isotopic compositions of H2O and dissolved inorganic carbon. Based on a calibrated 1-D radial flow model, reactive transport modeling was performed for the Frio-I Brine Pilot. A simple kinetic model of Fe release from the solid to aqueous phase was developed, which can reproduce the observed increases in aqueous Fe concentration. Brine samples collected after half a year had lower Fe concentrations due to carbonate precipitation, and this trend can be also captured by our modeling. The paper provides a method for estimating potential mobile Fe inventory, and its bounding concentration in the storage formation from limited observation data. Long-term simulations show that the CO2 plume gradually spreads outward due to capillary forces, and the gas saturation gradually decreases due to its dissolution and precipitation of carbonates. The gas phase is predicted to disappear after 500 years. Elevated aqueous CO2 concentrations remain for a longer time, but eventually decrease due to carbonate precipitation. For the Frio-I Brine Pilot, all injected CO2 could ultimately be sequestered as carbonate minerals. ?? 2010 Elsevier B.V.

High-accuracy determination of iron in seawater by isotope dilution multiple collector inductively coupled plasma mass spectrometry (ID-MC-ICP-MS) using nitrilotriacetic acid chelating resin for pre-concentration and matrix separation.

PubMed

de Jong, Jeroen; Schoemann, Véronique; Lannuzel, Delphine; Tison, Jean-Louis; Mattielli, Nadine

2008-08-15

In the present paper we describe a robust and simple method to measure dissolved iron (DFe) concentrations in seawater down to <0.1 nmol L(-1) level, by isotope dilution multiple collector inductively coupled plasma mass spectrometry (ID-MC-ICP-MS) using a (54)Fe spike and measuring the (57)Fe/(54)Fe ratio. The method provides for a pre-concentration step (100:1) by micro-columns filled with the resin NTA Superflow of 50 mL seawater samples acidified to pH 1.9. NTA Superflow is demonstrated to quantitatively extract Fe from acidified seawater samples at this pH. Blanks are kept low (grand mean 0.045+/-0.020 nmol L(-1), n=21, 3 x S.D. limit of detection per session 0.020-0.069 nmol L(-1) range), as no buffer is required to adjust the sample pH for optimal extraction, and no other reagents are needed than ultrapure nitric acid, 12 mM H(2)O(2), and acidified (pH 1.9) ultra-high purity (UHP) water. We measured SAFe (sampling and analysis of Fe) reference seawater samples Surface-1 (0.097+/-0.043 nmol L(-1)) and Deep-2 (0.91+/-0.17 nmol L(-1)) and obtained results that were in excellent agreement with their DFe consensus values: 0.118+/-0.028 nmol L(-1) (n=7) for Surface-1 and 0.932+/-0.059 nmol L(-1) (n=9) for Deep-2. We also present a vertical DFe profile from the western Weddell Sea collected during the Ice Station Polarstern (ISPOL) ice drift experiment (ANT XXII-2, RV Polarstern) in November 2004-January 2005. The profile shows near-surface DFe concentrations of approximately 0.6 nmol L(-1) and bottom water enrichment up to 23 nmol L(-1) DFe.

Enhancement of gold recovery using bioleaching from gold concentrate

NASA Astrophysics Data System (ADS)

Choi, S. H.; Cho, K. H.; Kim, B. J.; Choi, N. C.; Park, C. Y.

2012-04-01

The gold in refractory ores is encapsulated as fine particles (sometimes at a molecular level) in the crystal structure of the sulfide (typically pyrite with or without arsenopyrite) matrix. This makes it impossible to extract a significant amount of refractory gold by cyanidation since the cyanide solution cannot penetrate the pyrite/arsenopyrite crystals and dissolve gold particles, even after fine grinding. To effectively extract gold from these ores, an oxidative pretreatment is necessary to break down the sulfide matrix. The most popular methods of pretreatment include nitric acid oxidation, roasting, pressure oxidation and biological oxidation by microorganisms. This study investigated the bioleaching efficiency of Au concentrate under batch experimental conditions (adaptation cycles and chemical composition adaptation) using the indigenous acidophilic bacteria collected from gold mine leachate in Sunsin gold mine, Korea. We conducted the batch experiments at two different chemical composition (CuSO4 and ZnSO4), two different adaptation cycles 1'st (3 weeks) and 2'nd (6 weeks). The results showed that the pH in the bacteria inoculating sample decreased than initial condition and Eh increased. In the chemical composition adaptation case, the leached accumulation content of Fe and Pb was exhibited in CuSO4 adaptation bacteria sample more than in ZnSO4 adaptation bacteria samples, possibly due to pre-adaptation effect on chalcopyrite (CuFeS2) in gold concentrate. And after 21 days on the CuSO4 adaptation cycles case, content of Fe and Pb was appeared at 1'st adaptation bacteria sample(Fe - 1.82 and Pb - 25.81 times per control sample) lower than at 2'nd adaptation bacteria sample(Fe - 2.87 and Pb - 62.05 times per control sample). This study indicates that adaptation chemical composition and adaptation cycles can play an important role in bioleaching of gold concentrate in eco-/economic metallurgy process.

Cu-Ni-Fe anodes having improved microstructure

DOEpatents

Bergsma, S. Craig; Brown, Craig W.

2004-04-20

A method of producing aluminum in a low temperature electrolytic cell containing alumina dissolved in an electrolyte. The method comprises the steps of providing a molten electrolyte having alumina dissolved therein in an electrolytic cell containing the electrolyte. A non-consumable anode and cathode is disposed in the electrolyte, the anode comprised of Cu--Ni--Fe alloys having single metallurgical phase. Electric current is passed from the anode, through the electrolyte to the cathode thereby depositing aluminum on the cathode, and molten aluminum is collected from the cathode.

Photochemical-biological treatment of a real industrial biorecalcitrant wastewater containing 5-amino-6-methyl-2-benzimidazolone.

PubMed

Sarria, V; Parra, S; Invernizzi, M; Peringer, P; Pulgarin, C

2001-01-01

5-amino-6-methyl-2-benzimidazolone (AMBI), used in the manufacture of dyes, was characterised as a biorecalcitrant compound by means of different biodegradability tests. In order to enhance the biodegradability of this important pollutant, the application of Advanced Oxidation Process (AOPs) as a pretreatment was explored. Some experiments were addressed to find the most efficient AOP. The systems H2O2/hv, TiO2/H2O2/hv, Fe3+/hv, Fe3+/H2O2 and Fe3+/H2O2/hv were compared. The photo-Fenton system was the most efficient and the optimal conditions (AMBI, Fe3+, H2O2 concentrations) for the degradation of AMBI were found. During the photo-Fenton degradation, experiments were also made to obtain information concerning the evolution of: (a) organic carbon and initial compound concentration; (b) the oxidation state; (c) the toxicity; (d) the biodegradability; and (e) the chemical nature of the intermediates. These analyses show that the solution resulting from the treatment of AMBI is biologically compatible and complete mineralisation can be performed by biological means. A combined photochemical (Fenton) and biological flow reactor for the degradation of AMBI was successfully operated in continuous mode at laboratory scale. 100% of the initial concentration of AMBI and 80.3% of Dissolved Organic Carbon (DOC) were removed in 3.5 hours of total residence time. Finally, some field experiments under direct sunlight carried out at the Plataforma Solar de Almeria, Spain, demonstrated that this solar catalytic system is an effective treatment for this kind of industrial wastewater.

Effects of flooding on phosphorus and iron mobilization in highly weathered soils: Short-term effects and mechanisms

NASA Astrophysics Data System (ADS)

Maranguit, Deejay

2017-04-01

The strong affinity of phosphorus (P) to iron (Fe) oxides and hydroxides in highly weathered tropical soils limits P availability and therefore plant productivity. In flooded soils, however, P fixed by Fe oxides and hydroxides can be released and transformed to a more available form because of Fe3+ reduction to Fe2+. These P dynamics in flooded soils are well documented for rice paddies. Such effects are much less studied in other land-use types under the influence of seasonal flooding, especially in the tropics during heavy monsoon rains. The aim of this study was to investigate the mobilization of P during flooding leading to anaerobic conditions in topsoil and subsoil horizons depending on land-use type. Samples were collected in highly weathered soils from four replicate sites under natural rainforest, jungle rubber, rubber and oil palm plantations in Sumatra, Indonesia. Topsoil and subsoil were taken to ensure a wide range of soil organic matter (SOM) and P contents. Soils were incubated under anaerobic, flooded conditions at 30 ± 1 oC for 60 days. Our results confirmed the hypothesis that soil flooding mobilizes P and increases P availability. Two distinct and opposite phases, however, were observed upon flooding. During the first three weeks of flooding, the dissolved P (DP) concentration peaked, simultaneously with a peak of dissolved Fe2+ (DFe2+) and dissolved organic carbon (DOC) in the soil solution. After three weeks, P availability in soils decreased, although Fe-P and available P did not reach initial, pre-flooding levels. Accordingly, Fe dissolution and P mobilization were reversible processes. Furthermore, land-use type influenced the impacts of flooding on P and Fe forms mainly in the topsoil, where P dissolution and availability were generally higher under forest and, to a lesser extent, under jungle rubber. A positive correlation between DOC and DFe2+ (R2 = 0.42) in topsoil indicates that the intensity of microbially-mediated Fe3+ reduction is limited by the amount of available carbon (C) as an energy source for microorganisms. Moreover, microbial mineralization of organic P from SOM also increases P availability, and this process requires available C. This interpretation was supported by the strong correlation (R2 = 0.58) between available P and DOC, as well as between DP and DOC (R2 = 0.56) in topsoil. The increasing soil solution pH in topsoil and subsoil after flooding of all land-use types may also influence the P release over time. In summary, the increase of available P and DP during flooding is due to three main mechanisms: (1) P release via the microbially-mediated reductive dissolution of Fe3+ oxides; (2) P release during SOM mineralization and (3) solubility of Fe phosphate due to increasing pH. These mechanisms are relevant not only in riparian areas, where flooding occurs, but also in well-drained soil that is partly waterlogged after regular heavy rainfalls during the wet season. Likewise, the P cycle turnover is faster in compacted, often anaerobic plantation soils. Here, more P is pumped by the vegetation and then removed from plantations due to yield export.

Stability Behavior and Thermodynamic States of Iron and Manganese in Sandy Soil Aquifer, Manukan Island, Malaysia

DOE Office of Scientific and Technical Information (OSTI.GOV)

Lin, Chin Yik, E-mail: cy_lin_ars@hotmail.com; Abdullah, Mohd. Harun; Musta, Baba

2011-03-15

A total of 20 soil samples were collected from 10 boreholes constructed in the low lying area, which included ancillary samples taken from the high elevation area. Redox processes were investigated in the soil as well as groundwater in the shallow groundwater aquifer of Manukan Island, Sabah, Malaysia. Groundwater samples (n = 10) from each boreholes were also collected in the low lying area to understand the concentrations and behaviors of Fe and Mn in the dissolved state. This study strives to obtain a general understanding of the stability behaviors on Fe and Mn at the upper unsaturated and themore » lower-saturated soil horizons in the low lying area of Manukan Island as these elements usually play a major role in the redox chemistry of the shallow groundwater. Thermodynamic calculations using PHREEQC showed that the groundwater samples in the study area are oversaturated with respect to goethite, hematite, Fe(OH){sub 3} and undersaturated with respect to manganite and pyrochroite. Low concentrations of Fe and Mn in the groundwater might be probably due to the lack of minerals of iron and manganese oxides, which exist in the sandy aquifer. In fact, high organic matters that present in the unsaturated horizon are believed to be responsible for the high Mn content in the soil. It was observed that the soil samples collected from high elevation area (BK) comprises considerable amount of Fe in both unsaturated (6675.87 mg/kg) and saturated horizons (31440.49 mg/kg) compared to the low Fe content in the low lying area. Based on the stability diagram, the groundwater composition lies within the stability field for Mn{sup 2+} and Fe{sup 2+} under suboxic condition and very close to the FeS/Fe{sup 2+} stability boundary. This study also shows that both pH and Eh values comprise a strong negative value thus suggesting that the redox potential is inversely dependent on the changes of pH.« less

A mass balance approach to investigate arsenic cycling in a petroleum plume.

PubMed

Ziegler, Brady A; Schreiber, Madeline E; Cozzarelli, Isabelle M; Crystal Ng, G-H

2017-12-01

Natural attenuation of organic contaminants in groundwater can give rise to a series of complex biogeochemical reactions that release secondary contaminants to groundwater. In a crude oil contaminated aquifer, biodegradation of petroleum hydrocarbons is coupled with the reduction of ferric iron (Fe(III)) hydroxides in aquifer sediments. As a result, naturally occurring arsenic (As) adsorbed to Fe(III) hydroxides in the aquifer sediment is mobilized from sediment into groundwater. However, Fe(III) in sediment of other zones of the aquifer has the capacity to attenuate dissolved As via resorption. In order to better evaluate how long-term biodegradation coupled with Fe-reduction and As mobilization can redistribute As mass in contaminated aquifer, we quantified mass partitioning of Fe and As in the aquifer based on field observation data. Results show that Fe and As are spatially correlated in both groundwater and aquifer sediments. Mass partitioning calculations demonstrate that 99.9% of Fe and 99.5% of As are associated with aquifer sediment. The sediments act as both sources and sinks for As, depending on the redox conditions in the aquifer. Calculations reveal that at least 78% of the original As in sediment near the oil has been mobilized into groundwater over the 35-year lifespan of the plume. However, the calculations also show that only a small percentage of As (∼0.5%) remains in groundwater, due to resorption onto sediment. At the leading edge of the plume, where groundwater is suboxic, sediments sequester Fe and As, causing As to accumulate to concentrations 5.6 times greater than background concentrations. Current As sinks can serve as future sources of As as the plume evolves over time. The mass balance approach used in this study can be applied to As cycling in other aquifers where groundwater As results from biodegradation of an organic carbon point source coupled with Fe reduction. Copyright © 2017 Elsevier Ltd. All rights reserved.

A mass balance approach to investigate arsenic cycling in a petroleum plume

USGS Publications Warehouse

Ziegler, Brady A.; Schreiber, Madeline E.; Cozzarelli, Isabelle M.; Ng. G.-H. Crystal,

2017-01-01

Natural attenuation of organic contaminants in groundwater can give rise to a series of complex biogeochemical reactions that release secondary contaminants to groundwater. In a crude oil contaminated aquifer, biodegradation of petroleum hydrocarbons is coupled with the reduction of ferric iron (Fe(III)) hydroxides in aquifer sediments. As a result, naturally occurring arsenic (As) adsorbed to Fe(III) hydroxides in the aquifer sediment is mobilized from sediment into groundwater. However, Fe(III) in sediment of other zones of the aquifer has the capacity to attenuate dissolved As via resorption. In order to better evaluate how long-term biodegradation coupled with Fe-reduction and As mobilization can redistribute As mass in contaminated aquifer, we quantified mass partitioning of Fe and As in the aquifer based on field observation data. Results show that Fe and As are spatially correlated in both groundwater and aquifer sediments. Mass partitioning calculations demonstrate that 99.9% of Fe and 99.5% of As are associated with aquifer sediment. The sediments act as both sources and sinks for As, depending on the redox conditions in the aquifer. Calculations reveal that at least 78% of the original As in sediment near the oil has been mobilized into groundwater over the 35-year lifespan of the plume. However, the calculations also show that only a small percentage of As (∼0.5%) remains in groundwater, due to resorption onto sediment. At the leading edge of the plume, where groundwater is suboxic, sediments sequester Fe and As, causing As to accumulate to concentrations 5.6 times greater than background concentrations. Current As sinks can serve as future sources of As as the plume evolves over time. The mass balance approach used in this study can be applied to As cycling in other aquifers where groundwater As results from biodegradation of an organic carbon point source coupled with Fe reduction.

Microbial production of isotopically light iron(II) in a modern chemically precipitated sediment and implications for isotopic variations in ancient rocks

USGS Publications Warehouse

Tangalos, G.E.; Beard, B.L.; Johnson, C.M.; Alpers, Charles N.; Shelobolina, E.S.; Xu, H.; Konishi, H.; Roden, E.E.

2012-01-01

The inventories and Fe isotope composition of aqueous Fe(II) and solid-phase Fe compounds were quantified in neutral-pH, chemically precipitated sediments downstream of the Iron Mountain acid mine drainage site in northern California, USA. The sediments contain high concentrations of amorphous Fe(III) oxyhydroxides [Fe(III)am] that allow dissimilatory iron reduction (DIR) to predominate over Fe–S interactions in Fe redox transformation, as indicated by the very low abundance of Cr(II)-extractable reduced inorganic sulfur compared with dilute HCl-extractable Fe. δ56Fe values for bulk HCl- and HF-extractable Fe were ≈ 0. These near-zero bulk δ56Fe values, together with the very low abundance of dissolved Fe in the overlying water column, suggest that the pyrite Fe source had near-zero δ56Fe values, and that complete oxidation of Fe(II) took place prior to deposition of the Fe(III) oxide-rich sediment. Sediment core analyses and incubation experiments demonstrated the production of millimolar quantities of isotopically light (δ56Fe ≈ -1.5 to -0.5‰) aqueous Fe(II) coupled to partial reduction of Fe(III)am by DIR. Trends in the Fe isotope composition of solid-associated Fe(II) and residual Fe(III)am are consistent with experiments with synthetic Fe(III) oxides, and collectively suggest an equilibrium Fe isotope fractionation between aqueous Fe(II) and Fe(III)am of approximately -2‰. These Fe(III) oxide-rich sediments provide a model for early diagenetic processes that are likely to have taken place in Archean and Paleoproterozoic marine sediments that served as precursors for banded iron formations. Our results suggest pathways whereby DIR could have led to the formation of large quantities of low-δ56Fe minerals during BIF genesis.

Mechanical relaxations and 1/f noise in Bi, Nb, and Fe films

NASA Astrophysics Data System (ADS)

Alers, G. B.; Weissman, M. B.

1991-10-01

Anelastic piezoresistance and 1/f noise were measured in the same samples to compare mechanical relaxations with 1/f noise. In bismuth below 200 K, both effects could be fitted to a model invoking one class of mobile defects. In niobium, both the anelastic piezoresistance and the noise scaled with the concentration of dissolved hydrogen. A well-defined peak in noise versus temperature was observed without any peak in the anelastic response. In iron, noise apparently from a carbon Snoek relaxation was observed at 220 K in a sample with high impurity concentration and at 300 K with low impurity concentration. No anelastic feature was found at 220 K in the high-impurity-concentration sample. The broad nature of 1/f noise appears to arise not from a fundamental source but from the generally poor quality of thin films.

Importance of allochthonous and autochthonous dissolved organic matter in Fe(II) oxidation: A case study in Shizugawa Bay watershed, Japan.

PubMed

Lee, Ying Ping; Fujii, Manabu; Kikuchi, Tetsuro; Natsuike, Masafumi; Ito, Hiroaki; Watanabe, Toru; Yoshimura, Chihiro

2017-08-01

Ferrous iron (Fe[II]) oxidation by dissolved oxygen was investigated in the Shizugawa Bay watershed with particular attention given to the effect of dissolved organic matter (DOM) properties on Fe(II) oxidation. To cover a wide spectrum of DOM composition, water samples were collected from various water sources including freshwater (e.g., river water and wastewater effluent) and coastal seawater. Measurement of nanomolar Fe(II) oxidation by using luminol chemiluminescence under dark, air-saturated conditions at 25 °C indicated that spatio-temporal variation of the second-order rate constant (6.7-74.5 M -1  s -1 ) was partially explained by the variation of the sample pH (7.5-8.6). However, at comparable pH values, the oxidation rates for freshwater were generally greater than those for coastal seawater. The substantial decline in oxidation rate constant after the removal of humic-type (allochthonous) DOM suggested that this hydrophobic DOM is a key factor that accelerates the Fe(II) oxidation in the freshwater samples. Observed lower oxidation rates for coastal seawater compared with freshwater and organic ligand-free seawater were likely associated with microbially derived autochthonous DOM, and the variation of Fe(II) oxidation at a fixed pH was best described by fluorescence index that represents the proportion of autochthonous and allochthonous DOM in natural waters. Consistently, Fe(II) oxidation was found to be slower in the presence of cellular exudates from phytoplankton. The present study highlighted the significant effect of DOM composition on the Fe(II) oxidation in inland and coastal waters. Copyright © 2017 Elsevier Ltd. All rights reserved.

Sulfide mineralization: Its role in chemical weathering of Mars

NASA Technical Reports Server (NTRS)

Burns, Roger G.

1988-01-01

Pyrrhotite-pentlandite assemblages in mafic and ultramafic igneous rocks may have contributed significantly to the chemical weathering reactions that produced degradation products in the Martian regolith. By analogy with terrestrial processes, a model is proposed whereby supergene alteration of these primary Fe-Ni sulfides on Mars has generated secondary sulfides (e.g., pyrite) below the water table and produced acidic groundwater containing high concentrations of dissolved Fe, Ni and sulfate ions. The low pH solutions also initiated weathering reactions of igneous feldspars and ferromagnesian silicates to form clay silicate and ferric oxyhydroxide phases. Near-surface oxidation and hydrolysis of ferric sulfato- and hydroxo-complex ions and sols formed gossans above the water table consisting of poorly crystalline hydrated ferric sulfates (e.g., jarosite), oxides (ferrihydrite, goethite) and silica (opal). Underlying groundwater, now permafrost, contains hydroxo sulfato complexes of Fe, Al, Mg, Ni, etc., which may be stabilized in frozen acidic solutions beneath the surface of Mars. Sublimation of permafrost may replenish colloidal ferric oxides, sulfates and phyllosilicates during dust storms on Mars.

Weathering of sulfides on Mars

NASA Technical Reports Server (NTRS)

Burns, Roger G.; Fisher, Duncan S.

1987-01-01

Pyrrhotite-pentlandite assemblages in mafic and ultramafic igneous rocks may have contributed significantly to the chemical weathering reactions that produce degradation products in the Martian regolith. By analogy and terrestrial processes, a model is proposed whereby supergene alteration of these primary Fe-Ni sulfides on Mars has generated secondary sulfides (e.g., pyrite) below the water table and produced acidic groundwater containing high concentrations of dissolved Fe, Ni, and sulfate ions. The low pH solutions also initiated weathering reactions of igneous feldspars and ferromagnesian silicates to form clay silicate and ferric oxyhydroxide phases. Near-surface oxidation and hydrolysis of ferric sulfato-and hydroxo-complex ions and sols formed gossan above the water table consisting of poorly crystalline hydrated ferric sulfates (e.g., jarosite), oxides (ferrihydrite, goethite), and silica (opal). Underlying groundwater, now permafrost contains hydroxo sulfato complexes of Fe, Al, Mg, Ni, which may be stabilized in frozen acidic solutions beneath the surface of Mars. Sublimation of permafrost may replenish colloidal ferric oxides, sulfates, and phyllosilicates during dust storms on Mars.

Redox potential of shallow groundwater by 1-month continuous in situ potentiometric measurements

NASA Astrophysics Data System (ADS)

Ioka, Seiichiro; Muraoka, Hirofumi; Suzuki, Yota

2017-10-01

One-month continuous in situ potentiometric measurements of redox potential (Eh) were used to investigate the dominant redox processes in the shallow groundwater (i.e., <10 m) of a Holocene aquifer, Aomori City, northern Japan. The Eh values, which were determined using a platinum electrode, were -163, -169 and -173 mV, respectively, for three monitoring campaigns. The temperatures and pH values of shallow groundwater during all three periods were approximately 12 °C and 6.6, respectively. Dissolved oxygen and sulfide ion concentrations were not detected. Chemical analyses showed that the shallow groundwater is Na-Fe-HCO3 type, and contains over 40 mg/L of Fe (the dominant cation) and over 200 mg/L of HCO3 - (the dominant anion). A good fit was found between measured Eh values and Eh values calculated using thermodynamic data of fine-grained goethite. This suggests that Fe redox system is related to the Eh values of shallow groundwater in the Aomori City aquifer.

Experimental Investigation of Gas/Slag/Matte/Spinel Equilibria in the Cu-Fe-O-S-Si System at 1473 K (1200 °C) and P(SO2) = 0.25 atm

NASA Astrophysics Data System (ADS)

Hidayat, Taufiq; Fallah-Mehrjardi, Ata; Hayes, Peter C.; Jak, Evgueni

2018-04-01

New experimental data were obtained on the gas/slag/matte/spinel equilibria in the Cu-Fe-O-S-Si system at 1473 K (1200 °C) and P(SO2) = 0.25 atm covering Cu concentrations in matte between 42 and 78 wt pct Cu. Accurate measurements were obtained using high-temperature equilibration and the rapid quenching technique, followed by electron-probe X-ray microanalysis of equilibrium phase compositions. The use of spinel substrates made to support the samples ensures equilibrium with this primary phase solid, eliminates crucible contamination, and facilitates direct gas-condensed phase equilibrium and high quenching rates. Particular attention was given to the confirmation of the achievement of equilibrium. The results quantify the relationship between Cu in matte and oxygen partial pressure, sulfur in matte, oxygen in matte, Fe/SiO2 at slag liquidus, sulfur in slag, and dissolved copper in slag.

Effect of Silicon on Activity Coefficients of Platinum in Liquid Fe-Si, With Application to Core Formation

NASA Technical Reports Server (NTRS)

Righter, K.; Pando, K.; Danielson, L. R.; Humayun, M.

2017-01-01

Earth's core contains approximately 10% of a light element that is likely a combination of S, C, Si, and O, with Si possibly being the most abundant light element. Si dissolved into Fe liquids can have a large effect on the magnitude of the activity coefficient of siderophile elements (SE) in Fe liquids, and thus the partitioning behavior of those elements between core and mantle. The effect of Si can be small such as for Ni and Co, or large such as for Mo, Ge, Sb, As. The effect of Si on many siderophile elements is unknown yet could be an important, and as yet unquantified, influence on the core-mantle partitioning of SE. Here we report new experiments designed to quantify the effect of Si on the partitioning of Pt (with Re and Ru in progress or planned) between metal and silicate melt. The results will be applied to Earth, for which we have excellent constraints on the mantle Pt concentrations.

Effect of Silicon on Activity Coefficients of Siderophile Elements (P, Au, Pd, As, Ge, Sb, and In) in Liquid Fe, with Application to Core Formation

NASA Technical Reports Server (NTRS)

Righter, K.; Pando, K.; Danielson, L. R.; Humayun, M.; Righter, M.; Lapen, T.; Boujibar, A.

2016-01-01

Earth's core contains approximately 10 percent light elements that are likely a combination of S, C, Si, and O, with Si possibly being the most abundant. Si dissolved into Fe liquids can have a large effect on the magnitude of the activity coefficient of siderophile elements (SE) in Fe liquids, and thus the partitioning behavior of those elements between core and mantle. The effect of Si can be small such as for Ni and Co, or large such as for Mo, Ge, Sb, As. The effect of Si on many siderophile elements is unknown yet could be an important, and as yet unquantified, influence on the core-mantle partitioning of SE. Here we report new experiments designed to quantify the effect of Si on the partitioning of P, Au, Pd, and many other SE between metal and silicate melt. The results will be applied to Earth, for which we have excellent constraints on the mantle siderophile element concentrations.

Toward understanding the chloroquine action at the molecular level in antimalarial therapy--X-ray absorption studies in acetic acid solution.

PubMed

Walczak, Monika S; Lawniczak-Jablonska, Krystyna; Wolska, Anna; Sikora, Marcin; Sienkiewicz, Andrzej; Suárez, Liliana; Kosar, Aaron J; Bellemare, Marie-Josee; Bohle, D Scott

2011-04-21

The local atomic structure around the central iron of the synthetic soluble analog of malarial pigment in acetic acid solution and with addition of chloroquine as found by X-ray absorption spectroscopy is reported. The special interest was drawn to the axial linkage between the central iron atom of the ferriprotoporphyrin IX (FePPIX) coordinated axially to the propionate group of the adjacent FePPIX. This kind of bonding is typical for hematin anhydride. Detailed analysis revealed differences in oxygen coordination sphere (part of dimer linkage bond) between synthetic equivalent of hemozoin in the powder state and dissolved in acetic acid and water at different concentrations mimicking the physiological condition of the parasite's food vacuole. The results of performed studies suggest that the molecular structure of synthetic analogue of hemozoin is no longer dimer-like in acidic solution. Further changes in atomic order around Fe are seen after addition of the antimalarial drug chloroquine.

Geochemical control on the reduction of U(VI) to mononuclear U(IV) species in lacustrine sediments

NASA Astrophysics Data System (ADS)

Stetten, L.; Mangeret, A.; Brest, J.; Seder-Colomina, M.; Le Pape, P.; Ikogou, M.; Zeyen, N.; Thouvenot, A.; Julien, A.; Alcalde, G.; Reyss, J. L.; Bombled, B.; Rabouille, C.; Olivi, L.; Proux, O.; Cazala, C.; Morin, G.

2018-02-01

Contaminated systems in which uranium (U) concentrations slightly exceed the geochemical background are of particular interest to identify natural processes governing U trapping and accumulation in Earth's surface environments. For this purpose, we examined the role of early diagenesis on the evolution of U speciation and mobility in sediments from an artificial lake located downstream from a former mining site. Sediment and pore water chemistry together with U and Fe solid state speciation were analyzed in sediment cores sampled down to 50 cm depth at four locations in the lake. These organic-rich sediments (∼12% organic C) exhibited U concentrations in the 40-80 mg kg-1 range. The sediment columns were anoxic 2-3 mm below the sediment-water interface and pore waters pH was circumneutral. Pore water chemistry profiles showed that organic carbon mineralization was associated with Fe and Mn reduction and was correlated with a decrease in dissolved U concentration with depth. Immobilization of U in the sediment was correlated with the reduction of U(VI) to U(IV) at depth, as shown by U LIII-edge XANES spectroscopic analysis. XANES and EXAFS spectroscopy at the Fe K-edge showed the reduction of structural Fe(III) to Fe(II) in phyllosilicate minerals with depth, coincident with U(VI) to U(IV) reduction. Thermodynamic modeling suggests that Fe(II) could act as a major reducing agent for U(VI) during early diagenesis of these sediments, leading to complete U reduction below ∼30 cm depth. Shell-by-shell and Cauchy-Wavelet analysis of U LIII-EXAFS spectra indicates that U(VI) and U(IV) are mainly present as mononuclear species bound to C, P or Si ligands. Chemical extractions confirmed that ∼60-80% of U was present as non-crystalline species, which emphasizes that such species should be considered when evaluating the fate of U in lacustrine environments and the efficiency of sediment remediation strategies.

Geochemistry of ferromanganese nodules from DOMES site a, Northern Equatorial Pacific: Multiple diagenetic metal sources in the deep sea

USGS Publications Warehouse

Calvert, S.E.; Piper, D.Z.

1984-01-01

The major and minor element composition of ferromanganese nodules from DOMES Site A has been determined by X-ray fluorescence methods. Three phases appear to control the bulk compositions: Mn and Fe oxyhydroxides and aluminosilicates. Relatively wide compositional variations are evident throughout the area. Nodules with high Mn/Fe ratios, high Cu, Mg, Mo, Ni and Zn concentrations and high todorokite/??-MnO2 ratios have granular surface textures and are confined to an east-west trending depression with thin Quaternary sediment cover. Nodules with low Mn/Fe ratios, high concentrations of As, Ca, Ce, Co, La, P, Sr, Ti, V, Y and Zr and low todorokite/??-MnO2 ratios have smooth surfaces and are confined to shallower areas with relatively thick Quaternary sediment to the north and south of the depression. All nodules in the area have compositions which are influenced by diagenesis, but those with the most marked diagenetic signature (high Mn/Fe and Cu/Ni ratios, low Ce/La ratios and more todorokite) are found in areas of very slow or non-existent sedimentation; many of these nodules are actually in contact with outcropping Tertiary sediment. This paradox may be resolved by postulating, by analogy with some shallow-water occurrences, that the nodules accrete from bottom waters which have enhanced particulate and dissolved metal contents derived from diagenetic reaction in areas remote from the site of nodule formation. The metals are supplied in a bottom flow (probably Antarctic Bottom Water) which also erodes, or prevents modern sedimentation in, the depression. Nodules on the flanks of the depression are not evidently affected by this flow and derive at least pan of their constituent metals from diagenetic reaction in the underlying Quaternary sediment. Apparently, abyssal diagenetic nodules can have an immediate and a remote diagenetic metal source. Metal fluxes derived from pore water dissolved metal gradients may not be relevant to particular accreting nodules if a significant fraction of their metals is derived from outside the area in which they form. ?? 1984.

Ferric iron in sediments as a novel CO2 mineral trap: CO 2-SO2 reaction with hematite

USGS Publications Warehouse

Palandri, J.L.; Rosenbauer, R.J.; Kharaka, Y.K.

2005-01-01

Thermodynamic simulations of reactions among SO2-bearing CO 2-dominated gas, water and mineral phases predict that Fe III in sediments should be converted almost entirely to dissolved FeII and siderite (FeCO3), and that SO2 should simultaneously be oxidized to dissolved sulfate. The reactions are however, subject to kinetic constraints which may result in deviation from equilibrium and the precipitation of other metastable mineral phases. To test the prediction, a laboratory experiment was carried out in a well stirred hydrothermal reactor at 150??C and 300 bar with hematite, 1.0 m NaCl, 0.5 m NaOH, SO2 in quantity sufficient to reduce much of the iron, and excess CO2. The experiment produced stable siderite and metastable pyrite and elemental S. Changes in total dissolved Fe are consistent with nucleation of pyrite at ???17 h, and nucleation of siderite at ???600 h. Dissolution features present on elemental S at the conclusion of the experiment suggest nucleation early in the experiment. The experiment did not reach equilibrium after ???1400 h, as indicated by coexistence of hematite with metastable pyrite and elemental sulfur. However, the results confirm that FeIII can be used to trap CO2 in siderite if partly oxidized S, as SO2, is present to reduce the Fe with CO2 in the gas phase. ?? 2005 Elsevier Ltd. All rights reserved.

Phosphate and phytate adsorption and precipitation on ferrihydrite surfaces

DOE Office of Scientific and Technical Information (OSTI.GOV)

Wang, Xiaoming; Hu, Yongfeng; Tang, Yadong

Phosphorous (P) sorption on mineral surfaces largely controls P mobility and bioavailability, hence its pollution potential, but the sorption speciation and mechanism remain poorly understood. In this study, we have identified and quantified the speciation of both phosphate and phytate sorbed on ferrihydrite with various P loadings at pH 3–8 using differential atomic pair distribution function (d-PDF) analysis, synchrotron-based X-ray diffraction (XRD), and P and Fe K-edge X-ray absorption near edge structure (XANES) and attenuated total reflectance-Fourier transform infrared (ATR-FTIR) spectroscopy. With increasing P sorption loading for both phosphate and phytate, the sorption mechanism transits from bidentate-binuclear surface complexation tomore » unidentified ternary complexation and to precipitation of amorphous FePO 4 and amorphous Fe-phytate. At a given P sorption loading, phosphate precipitates more readily than phytate. Both phosphate and phytate promote ferrihydrite dissolution with phytate more intensively, but the dissolved FeIII concentration in the bulk solution is low because the majority of the released Fe III precipitate with the anions. Results also show that amorphous FePO 4 and amorphous Fe-phytate have similar PO 4 local coordination environment. In conclusion, these new insights into the P surface complexation and precipitation, and the ligand-promoted dissolution behavior improve our understanding of P fate in soils, aquatic environment and water treatment systems as mediated by mineral-water interfacial reactions.« less

Phosphate and phytate adsorption and precipitation on ferrihydrite surfaces

DOE PAGES

Wang, Xiaoming; Hu, Yongfeng; Tang, Yadong; ...

2017-09-26

Phosphorous (P) sorption on mineral surfaces largely controls P mobility and bioavailability, hence its pollution potential, but the sorption speciation and mechanism remain poorly understood. In this study, we have identified and quantified the speciation of both phosphate and phytate sorbed on ferrihydrite with various P loadings at pH 3–8 using differential atomic pair distribution function (d-PDF) analysis, synchrotron-based X-ray diffraction (XRD), and P and Fe K-edge X-ray absorption near edge structure (XANES) and attenuated total reflectance-Fourier transform infrared (ATR-FTIR) spectroscopy. With increasing P sorption loading for both phosphate and phytate, the sorption mechanism transits from bidentate-binuclear surface complexation tomore » unidentified ternary complexation and to precipitation of amorphous FePO 4 and amorphous Fe-phytate. At a given P sorption loading, phosphate precipitates more readily than phytate. Both phosphate and phytate promote ferrihydrite dissolution with phytate more intensively, but the dissolved FeIII concentration in the bulk solution is low because the majority of the released Fe III precipitate with the anions. Results also show that amorphous FePO 4 and amorphous Fe-phytate have similar PO 4 local coordination environment. In conclusion, these new insights into the P surface complexation and precipitation, and the ligand-promoted dissolution behavior improve our understanding of P fate in soils, aquatic environment and water treatment systems as mediated by mineral-water interfacial reactions.« less

Arsenic cycling in hydrocarbon plumes: secondary effects of natural attenuation

USGS Publications Warehouse

Cozzarelli, Isabelle M.; Schreiber, Madeline E.; Erickson, Melinda L.; Ziegler, Brady A.

2016-01-01

Monitored natural attenuation is widely applied as a remediation strategy at hydrocarbon spill sites. Natural attenuation relies on biodegradation of hydrocarbons coupled with reduction of electron acceptors, including solid phase ferric iron (Fe(III)). Because arsenic (As) adsorbs to Fe-hydroxides, a potential secondary effect of natural attenuation of hydrocarbons coupled with Fe(III) reduction is a release of naturally occurring As to groundwater. At a crude-oil-contaminated aquifer near Bemidji, Minnesota, anaerobic biodegradation of hydrocarbons coupled to Fe(III) reduction has been well documented. We collected groundwater samples at the site annually from 2009 to 2013 to examine if As is released to groundwater and, if so, to document relationships between As and Fe inside and outside of the dissolved hydrocarbon plume. Arsenic concentrations in groundwater in the plume reached 230 µg/L, whereas groundwater outside the plume contained less than 5 µg/L As. Combined with previous data from the Bemidji site, our results suggest that (1) naturally occurring As is associated with Fe-hydroxides present in the glacially derived aquifer sediments; (2) introduction of hydrocarbons results in reduction of Fe-hydroxides, releasing As and Fe to groundwater; (3) at the leading edge of the plume, As and Fe are removed from groundwater and retained on sediments; and (4) downgradient from the plume, patterns of As and Fe in groundwater are similar to background. We develop a conceptual model of secondary As release due to natural attenuation of hydrocarbons that can be applied to other sites where an influx of biodegradable organic carbon promotes Fe(III) reduction.

Temperature dependence and coupling of iron and arsenic reduction and release during flooding of a contaminated soil.

PubMed

Weber, Frank-Andreas; Hofacker, Anke F; Voegelin, Andreas; Kretzschmar, Ruben

2010-01-01

Arsenic (As) in soils and sediments is commonly mobilized when anoxic conditions promote microbial iron (Fe) and As reduction. Recent laboratory studies and field observations have suggested a decoupling between Fe and As reduction and release, but the links between these processes are still not well understood. In microcosm experiments, we monitored the formation of Fe(II) and As(III) in the porewater and in the soil solid-phase during flooding of a contaminated floodplain soil at temperatures of 23, 14, and 5 degrees C. At all temperatures, flooding induced the development of anoxic conditions and caused increasing concentrations of dissolved Fe(II) and As(III). Decreasing the temperature from 23 to 14 and 5 degrees C strongly slowed down soil reduction and Fe and As release. Speciation of As in the soil solid-phase by X-ray absorption spectroscopy (XAS) and extraction of the Fe(II) that has formed by reductive Fe(III) (hydr)oxide dissolution revealed that less than 3.9% of all As(III) and less than 3.2% of all Fe(II) formed during 52 days of flooding at 23 degrees C were released into the porewater, although 91% of the initially ascorbate-extractable Fe and 66% of the total As were reduced. The amount of total As(III) formed during soil reduction was linearly correlated to the amount of total Fe(II) formed, indicating that the rate of As(V) reduction was controlled by the rate of microbial Fe(III) (hydr)oxide reduction.

Arsenic Cycling in Hydrocarbon Plumes: Secondary Effects of Natural Attenuation.

PubMed

Cozzarelli, Isabelle M; Schreiber, Madeline E; Erickson, Melinda L; Ziegler, Brady A

2016-01-01

Monitored natural attenuation is widely applied as a remediation strategy at hydrocarbon spill sites. Natural attenuation relies on biodegradation of hydrocarbons coupled with reduction of electron acceptors, including solid phase ferric iron (Fe(III)). Because arsenic (As) adsorbs to Fe-hydroxides, a potential secondary effect of natural attenuation of hydrocarbons coupled with Fe(III) reduction is a release of naturally occurring As to groundwater. At a crude-oil-contaminated aquifer near Bemidji, Minnesota, anaerobic biodegradation of hydrocarbons coupled to Fe(III) reduction has been well documented. We collected groundwater samples at the site annually from 2009 to 2013 to examine if As is released to groundwater and, if so, to document relationships between As and Fe inside and outside of the dissolved hydrocarbon plume. Arsenic concentrations in groundwater in the plume reached 230 µg/L, whereas groundwater outside the plume contained less than 5 µg/L As. Combined with previous data from the Bemidji site, our results suggest that (1) naturally occurring As is associated with Fe-hydroxides present in the glacially derived aquifer sediments; (2) introduction of hydrocarbons results in reduction of Fe-hydroxides, releasing As and Fe to groundwater; (3) at the leading edge of the plume, As and Fe are removed from groundwater and retained on sediments; and (4) downgradient from the plume, patterns of As and Fe in groundwater are similar to background. We develop a conceptual model of secondary As release due to natural attenuation of hydrocarbons that can be applied to other sites where an influx of biodegradable organic carbon promotes Fe(III) reduction. © 2015, National Ground Water Association.

Trace metals in bulk precipitation and throughfall in a suburban area of Japan

NASA Astrophysics Data System (ADS)

Hou, H.; Takamatsu, T.; Koshikawa, M. K.; Hosomi, M.

Throughfall and bulk precipitation samples were collected monthly for 1.5 years over bare land and under canopies of Japanese cedar ( Cryptomeria japonica), Japanese red pine ( Pinus densiflora), Japanese cypress ( Chamaecyparis obtusa), and bamboo-leafed oak ( Quercus myrsinaefolia) in a suburban area of Japan. Samples were analyzed for dissolved Al, Mn, Fe, Cu, Zn, Ag, In, Sn, Sb and Bi by ICP-AES and ICP-MS. The metal concentrations were higher in throughfall, especially that of C. japonica, than bulk precipitation. Enrichment ratios (ERs: ratios of metal concentrations in throughfall to those in bulk precipitation) ranged from 2.5 (Zn) to 5.3 (Ag) (3.9 on average), and ERs for slightly soluble metals were generally higher than those for easily soluble metals. Concentrations of Mn, Fe, Cu, and Zn accounted for 99% of the total concentration of heavy metals in rainwater, whereas those of rare metals such as Ag, In, Sn, and Bi totaled <0.23%. Average concentrations of rare metals were 0.002 and 0.010 μg l -1 for Ag, 0.001 and 0.005 μg l -1 for In, 0.062 and 0.21 μg l -1 for Sn, and 0.006 and 0.023 μg l -1 for Bi in bulk precipitation and throughfall, respectively. The metal concentrations in rainwater were negatively correlated to the volume of rainwater, indicating that washout is the main mechanism that incorporates metals into rainwater. From the enrichment factors, that is, (X/Al) rain/(X/Al) crust, metals other than Fe were shown to be more enriched in rainwater than in the Earth's crust, including those present as a result of leaching from soil dust (Mn) and from anthropogenic sources (Cu, Zn, Ag, In, Sn, Sb, and Bi).

The Effect of Metal Composition on Fe-Ni Partition Behavior between Olivine and FeNi-Metal, FeNi-Carbide, FeNi-Sulfide at Elevated Pressure

NASA Technical Reports Server (NTRS)

Holzheid, Astrid; Grove, Timothy L.

2005-01-01

Metal-olivine Fe-Ni exchange distribution coefficients were determined at 1500 C over the pressure range of 1 to 9 GPa for solid and liquid alloy compositions. The metal alloy composition was varied with respect to the Fe/Ni ratio and the amount of dissolved carbon and sulfur. The Fe/Ni ratio of the metal phase exercises an important control on the abundance of Ni in the olivine. The Ni abundance in the olivine decreases as the Fe/Ni ratio of the coexisting metal increases. The presence of carbon (up to approx. 3.5 wt.%) and sulfur (up to approx. 7.5 wt.%) in solution in the liquid Fe-Ni-metal phase has a minor effect on the partitioning of Fe and Ni between metal and olivine phases. No pressure dependence of the Fe-Ni-metal-olivine exchange behavior in carbon- and sulfur-free and carbon- and sulfur-containing systems was found within the investigated pressure range. To match the Ni abundance in terrestrial mantle olivine, assuming an equilibrium metal-olivine distribution, a sub-chondritic Fe/Ni-metal ratio that is a factor of 17 to 27 lower than the Fe/Ni ratios in estimated Earth core compositions would be required, implying higher Fe concentrations in the core forming metal phase. A simple metal-olivine equilibrium distribution does not seem to be feasible to explain the Ni abundances in the Earth's mantle. An equilibrium between metal and olivine does not exercise a control on the problem of Ni overabundance in the Earth's mantle. The experimental results do not contradict the presence of a magma ocean at the time of terrestrial core formation, if olivine was present in only minor amounts at the time of metal segregation.

Iron as a Cofactor That Limits the Promotion of Cyanobacteria in Lakes Across a Tropic Gradient

NASA Astrophysics Data System (ADS)

Sorichetti, R. J.; Creed, I. F.; Trick, C. G.

2014-12-01

The frequency and intensity of cyanobacterial blooms (cyanoblooms) is increasing globally. While cyanoblooms in eutrophic (nutrient-rich) freshwater lakes are expected to persist and worsen with climate change projections, many of the "new" cyanobloom reports pertain to oligotrophic (nutrient-poor) freshwater lakes with no prior history of cyanobloom occurrence. Under the pressures of a changing climate, there exists a critical research need to revisit existing conceptual models and identify cyanobloom regulating factors currently unaccounted for. Iron (Fe) is required in nearly all pathways of cyanobacterial macronutrient use, though its precise role in regulating cyanobacterial biomass across the lake trophic gradient is not fully understood. The hypotheses tested were: (1) cyanobacteria will predominate in lakes when bioavailable Fe concentration is low, and (2) cyanobacteria overcome this Fe limitation in all lakes using the siderophore-based Fe acquisition strategy to scavenge Fe providing a competitive advantage over other phytoplankton. These hypotheses were tested using natural lakes across an oligo-meso-eutrophic gradient across Canada. In all lakes sampled, the relative cyanobacterial biomass was highest at low predicted Fe bioavailability (< 1.0 × 10-19 mol L-1). Within this range of low bioavailable Fe, iron-binding organic ligands were measured. Concentrations of ligands with reactive hydroxamate moieties were positively correlated to cyanobacterial biomass in both the oligotrophic (r2 = 0.77, p < 0.001) and eutrophic (r2 = 0.81, p < 0.001) lakes suggesting a possible low-Fe mediated cellular origin, siderophores. Fe-binding ligands with catecholate-type binding sites were detected in all lakes, although lack of a relationship with cyanobacterial biomass and a significant relationship with dissolved organic carbon (DOC) in oligotrophic (r2 = 0.65, p < 0.001) and eutrophic (r2 = 0.65, p < 0.001) lakes may indicate an allochthonous source that is not used by cyanobacteria. These findings suggest that Fe serves as a possible cofactor that maintains cyanobacterial levels across a lake trophic gradient and that cyanobacteria invoke a similar Fe-scavenging system to overcome Fe limitation in lakes of all trophic status.

Cation-induced coagulation of aquatic plant-derived dissolved organic matter: Investigation by EEM-PARAFAC and FT-IR spectroscopy.

PubMed

Liu, Shasha; Zhu, Yuanrong; Liu, Leizhen; He, Zhongqi; Giesy, John P; Bai, Yingchen; Sun, Fuhong; Wu, Fengchang

2018-03-01

Complexation and coagulation of plant-derived dissolved organic matter (DOM) by metal cations are important biogeochemical processes of organic matter in aquatic systems. Thus, coagulation and fractionation of DOM derived from aquatic plants by Ca(II), Al(III), and Fe(III) ions were investigated. Metal ion-induced removal of DOM was determined by analyzing dissolved organic carbon in supernatants after addition of these metal cations individually. After additions of metal ions, both dissolved and coagulated organic fractions were characterized by use of fluorescence excitation emission matrix-parallel factor (EEM-PARAFAC) analysis and Fourier transform infrared (FT-IR) spectroscopy. Addition of Ca(II), Fe(III) or Al(III) resulted in net removal of aquatic plant-derived DOM. Efficiencies of removal of DOM by Fe(III) or Al(III) were greater than that by Ca(II). However, capacities to remove plant-derived DOM by the three metals were less than which had been previously reported for humic materials. Molecular and structural features of plant-derived DOM fractions in associations with metal cations were characterized by changes in fluorescent components and infrared absorption peaks. Both aromatic and carboxylic-like organic matters could be removed by Ca(II), Al(III) or Fe(III) ions. Whereas organic matters containing amides were preferentially removed by Ca(II), and phenolic materials were selectively removed by Fe(III) or Al(III). These observations indicated that plant-derived DOM might have a long-lasting effect on water quality and organisms due to its poor coagulation with metal cations in aquatic ecosystems. Plant-derived DOM is of different character than natural organic matter and it is not advisable to attempt removal through addition of metal salts during treatment of sewage. Copyright © 2017 Elsevier Ltd. All rights reserved.

Inverse geochemical modeling of groundwater evolution with emphasis on arsenic in the Mississippi River Valley alluvial aquifer, Arkansas (USA)

USGS Publications Warehouse

Sharif, M.U.; Davis, R.K.; Steele, K.F.; Kim, B.; Kresse, T.M.; Fazio, J.A.

2008-01-01

Inverse geochemical modeling (PHREEQC) was used to identify the evolution of groundwater with emphasis on arsenic (As) release under reducing conditions in the shallow (25-30 m) Mississippi River Valley Alluvial aquifer, Arkansas, USA. The modeling was based on flow paths defined by high-precision (??2 cm) water level contour map; X-ray diffraction (XRD), scanning electron microscopic (SEM), and chemical analysis of boring-sediments for minerals; and detailed chemical analysis of groundwater along the flow paths. Potential phases were constrained using general trends in chemical analyses data of groundwater and sediments, and saturation indices data (MINTEQA2) of minerals in groundwater. Modeling results show that calcite, halite, fluorite, Fe oxyhydroxide, organic matter, H2S (gas) were dissolving with mole transfers of 1.40E - 03, 2.13E - 04, 4.15E - 06, 1.25E + 01, 3.11, and 9.34, respectively along the dominant flow line. Along the same flow line, FeS, siderite, and vivianite were precipitating with mole transfers of 9.34, 3.11, and 2.64E - 07, respectively. Cation exchange reactions of Ca2+ (4.93E - 04 mol) for Na+ (2.51E - 04 mol) on exchange sites occurred along the dominant flow line. Gypsum dissolution reactions were dominant over calcite dissolution in some of the flow lines due to the common ion effect. The concentration of As in groundwater ranged from <0.5 to 77 ??g/L. Twenty percent total As was complexed with Fe and Mn oxyhydroxides. The redox environment, chemical data of sediments and groundwater, and the results of inverse geochemical modeling indicate that reductive dissolution of Fe oxyhydroxide is the dominant process of As release in the groundwater. The relative rate of reduction of Fe oxyhydroxide over SO42 - with co-precipitation of As into sulfide is the limiting factor controlling dissolved As in groundwater. ?? 2007 Elsevier B.V. All rights reserved.

Flushing of distal hillslopes as an alternative source of stream dissolved organic carbon in a headwater catchment

USGS Publications Warehouse

Gannon, John P; Bailey, Scott W.; McGuire, Kevin J.; Shanley, James B.

2015-01-01

We investigated potential source areas of dissolved organic carbon (DOC) in headwater streams by examining DOC concentrations in lysimeter, shallow well, and stream water samples from a reference catchment at the Hubbard Brook Experimental Forest. These observations were then compared to high-frequency temporal variations in fluorescent dissolved organic matter (FDOM) at the catchment outlet and the predicted spatial extent of shallow groundwater in soils throughout the catchment. While near-stream soils are generally considered a DOC source in forested catchments, DOC concentrations in near-stream groundwater were low (mean = 2.4 mg/L, standard error = 0.6 mg/L), less than hillslope groundwater farther from the channel (mean = 5.7 mg/L, standard error = 0.4 mg/L). Furthermore, water tables in near-stream soils did not rise into the carbon-rich upper B or O horizons even during events. In contrast, soils below bedrock outcrops near channel heads where lateral soil formation processes dominate had much higher DOC concentrations. Soils immediately downslope of bedrock areas had thick eluvial horizons indicative of leaching of organic materials, Fe, and Al and had similarly high DOC concentrations in groundwater (mean = 14.5 mg/L, standard error = 0.8 mg/L). Flow from bedrock outcrops partially covered by organic soil horizons produced the highest groundwater DOC concentrations (mean = 20.0 mg/L, standard error = 4.6 mg/L) measured in the catchment. Correspondingly, stream water in channel heads sourced in part by shallow soils and bedrock outcrops had the highest stream DOC concentrations measured in the catchment. Variation in FDOM concentrations at the catchment outlet followed water table fluctuations in shallow to bedrock soils near channel heads. We show that shallow hillslope soils receiving runoff from organic matter-covered bedrock outcrops may be a major source of DOC in headwater catchments in forested mountainous regions where catchments have exposed or shallow bedrock near channel heads.

Microscale speciation of arsenic and iron in ferric-based sorbents subjected to simulated landfill conditions

PubMed Central

Root, Robert A.; Fathordoobadi, Sahar; Alday, Fernando; Ela, Wendell; Chorover, Jon

2013-01-01

During treatment for potable use, water utilities generate arsenic-bearing ferric wastes that are subsequently dispatched to landfills. The biogeochemical weathering of these residuals in mature landfills affects the potential mobilization of sorbed arsenic species via desorption from solids subjected to phase transformations driven by abundant organic matter and bacterial activity. Such processes are not simulated with the Toxicity Characteristic Leaching Procedure (TCLP) currently used to characterize hazard. To examine the effect of sulfate on As retention in landfill leachate, columns of As(V) loaded amorphous ferric hydroxide were reacted biotically at two leachate sulfate concentrations (0.064 mM and 2.1 mM). After 300 d, ferric sorbents were reductively dissolved. Arsenic released to porewaters was partially co-precipitated in mixed-valent secondary iron phases whose speciation was dependent on sulfate concentration. As and Fe XAS showed that, in the low sulfate column, 75–81% of As(V) was reduced to As(III), and 53–68% of the Fe(III) sorbent was transformed, dominantly to siderite and green rust. In the high sulfate column, Fe(III) solids were reduced principally to FeS(am), whereas As(V) was reduced to a polymeric sulfide with local atomic structure of realgar. Multi-energy micro-X-ray fluorescence (ME-μXRF) imaging at Fe and As K-edges showed that As formed surface complexes with ferrihydrite > siderite > green rust in the low sulfate column; while discrete realgar-like phases formed in the high sulfate systems. Results indicate that landfill sulfur chemistry exerts strong control over the potential mobilization of As from ferric sorbent residuals by controlling secondary As and Fe sulfide co-precipitate formation. PMID:24102155

Application of iron and zinc isotopes to track the sources and mechanisms of metal loading in a mountain watershed

USGS Publications Warehouse

Borrok, D.M.; Wanty, R.B.; Ian, Ridley W.; Lamothe, P.J.; Kimball, B.A.; Verplanck, P.L.; Runkel, R.L.

2009-01-01

Here the hydrogeochemical constraints of a tracer dilution study are combined with Fe and Zn isotopic measurements to pinpoint metal loading sources and attenuation mechanisms in an alpine watershed impacted by acid mine drainage. In the tested mountain catchment, ??56Fe and ??66Zn isotopic signatures of filtered stream water samples varied by ???3.5??? and 0.4???, respectively. The inherent differences in the aqueous geochemistry of Fe and Zn provided complimentary isotopic information. For example, variations in ??56Fe were linked to redox and precipitation reactions occurring in the stream, while changes in ??66Zn were indicative of conservative mixing of different Zn sources. Fen environments contributed distinctively light dissolved Fe (<-2.0???) and isotopically heavy suspended Fe precipitates to the watershed, while Zn from the fen was isotopically heavy (>+0.4???). Acidic drainage from mine wastes contributed heavier dissolved Fe (???+0.5???) and lighter Zn (???+0.2???) isotopes relative to the fen. Upwelling of Fe-rich groundwater near the mouth of the catchment was the major source of Fe (??56Fe ??? 0???) leaving the watershed in surface flow, while runoff from mining wastes was the major source of Zn. The results suggest that given a strong framework for interpretation, Fe and Zn isotopes are useful tools for identifying and tracking metal sources and attenuation mechanisms in mountain watersheds. ?? 2009 Elsevier Ltd.

Opposite effects of dissolved oxygen on the removal of As(III) and As(V) by carbonate structural Fe(II).

PubMed

Tian, Zeyuan; Feng, Yong; Guan, Yiyi; Shao, Binbin; Zhang, Yalei; Wu, Deli

2017-12-05

Freshly prepared carbonate structural Fe(II) (CSF) was used to immobilize As(III) and As(V) in wastewater under oxic and anoxic conditions. Dissolved oxygen was found to exert opposite effects on these two arsenic species. The sorption density of As(III) was higher under oxic conditions, whereas that of As(V) was higher under anoxic conditions. X-ray diffraction and infrared spectroscopic analyses indicated that crystalline parasymplesite (Fe(II) 3 (AsO 4 ) 2 ·8H 2 O) was formed when As(V) was removed under anoxic conditions, while an amorphous Fe-As-containing precipitate was formed when As(III) was removed under oxic conditions. The distribution of arsenic and iron between the solution and sediments suggested that the oxidation of structural Fe(II) promoted coprecipitation process and inhibited surface complexation. X-ray photoelectron spectroscopic analyses revealed that more As(III) was oxidized under oxic condition, which contributed to a higher sorption capacity for As(III). The formation of parasymplesite through surface complexation/precipitation was proposed to be more effective for the removal of As(V) by CSF, while As(III) was more efficiently removed through coprecipitation. Together, the results suggest that CSF may be an effective material for sequestering both As(III) and As(V). In addition, attention should be paid to the dissolved oxygen content when remediating different arsenic species.

Characterization of Fe(II) oxidizing bacterial activities and communities at two acidic Appalachian coalmine drainage-impacted sites

DOE Office of Scientific and Technical Information (OSTI.GOV)

Senko, John M.; Wanjugi, Pauline; Lucas, Melanie

2008-06-12

We characterized the microbiologically mediated oxidative precipitation of Fe(II) from coalminederived acidic mine drainage (AMD) along flow-paths at two sites in northern Pennsylvania. At the Gum Boot site, dissolved Fe(II) was efficiently removed from AMD whereas minimal Fe(II) removal occurred at the Fridays-2 site. Neither site received human intervention to treat the AMD. Culturable Fe(II) oxidizing bacteria were most abundant at sampling locations along the AMD flow path corresponding to greatest Fe(II) removal and where overlying water contained abundant dissolved O2. Rates of Fe(II) oxidation determined in laboratory-based sediment incubations were also greatest at these sampling locations. Ribosomal RNA intergenicmore » spacer analysis and sequencing of partial 16S rRNA genes recovered from sediment bacterial communities revealed similarities among populations at points receiving regular inputs of Fe(II)-rich AMD and provided evidence for the presence of bacterial lineages capable of Fe(II) oxidation. A notable difference between bacterial communities at the two sites was the abundance of Chloroflexi-affiliated 16S rRNA gene sequences in clone libraries derived from the Gum Boot sediments. Our results suggest that inexpensive and reliable AMD treatment strategies can be implemented by mimicking the conditions present at the Gum Boot field site.« less

Seasonal variation and sources of dissolved trace metals in Maó Harbour, Minorca Island.

PubMed

Martínez-Soto, Marly C; Tovar-Sánchez, Antonio; Sánchez-Quiles, David; Rodellas, Valentí; Garcia-Orellana, Jordi; Basterretxea, Gotzon

2016-09-15

The environmental conditions of semi-enclosed coastal water-bodies are directly related to the catchment, human activities, and oceanographic setting in which they are located. As a result of low tidal forcing, and generally weak currents, waters in Mediterranean harbours are poorly renewed, leading to quality deterioration. Here, we characterise the seasonal variation of trace metals (i.e. Co, Cd, Cu, Fe, Mo, Ni, Pb, and Zn) in surface waters, and trace metal content in sediments from Maó Harbour, a semi-enclosed coastal ecosystem in the NW Mediterranean Sea. Our results show that most of the dissolved trace metals in the waters of Maó Harbour exhibit a marked inner-outer concentration gradient, suggesting a permanent input into the inner part of the harbour. In general, metal concentrations in the waters of Maó Harbour are higher than those in offshore waters. Concentration of Cu (21±8nM), Fe (9.2±3.2nM) and Pb (1.3±0.4nM) are particularly high when compared with other coastal areas of the Mediterranean Sea. The concentration of some metals such as Cu and Zn increases during summertime, when the human population and boat traffic increase during the tourism season, and when resuspension from the metal enriched sediments is higher. The evaluation of the metal sources in the harbour reveals that, compared with other putative sources such as runoff, aerosol deposition and fresh groundwater discharges, contaminated sediments are the main source of the metals found in the water column, most likely through vessel-driven resuspension events. This study contributes to the understanding of the processes that control the occurrence and distribution of trace metals in Maó Harbour, thus aiding in the effective management of the harbour, and enhancing the overall quality of the seawater ecosystem. Copyright © 2016 Elsevier B.V. All rights reserved.

Habitability from the Surface to the Deep

NASA Astrophysics Data System (ADS)

Cox, A. D.; Schmidt, R.; Dahlquist, G. R.; Foster, J.; Dillard, M.

2016-12-01

Merging aqueous geochemical parameters of habitability with microbial identity and activity will help determine microbial contributions to observed water-rock reactions in surface to deep environments. To determine habitability for microbial life and decipher mechanisms by which microbes survive and perform chemical reactions, over one hundred sites in diverse geological and geochemical environs have been sampled for aqueous geochemistry, mineralogy, and microbial identity and activity. Sites ranged from surficial creeks and rivers to the flooded mine shafts beneath to hydrothermal features in the caldera of a supervolcano 250 km distant; these environments contain metal scarcity, extreme anoxia, and wide variations in metal, organic carbon, and oxygen scarcity, respectively. Aqueous geochemistry included in situ measurement of temperature, pH, conductivity, and dissolved oxygen by meters; field spectrophotometry for redox active species; and synchronous sample collection and preservation for water isotopes, major cations and anions, trace elements, and dissolved inorganic and organic carbon, and more. Concurrent collection and preservation of planktonic and sediment biomass at each site will allow for microbial community identification and assessment of microbial activity. DNA extraction and PCR amplification using universal, eukaryotic, bacterial, and archaeal small subunit ribosomal RNA gene primers yielded products for sequencing. For many of the aqueous geochemical parameters analyzed, including Li and B, concentrations in flooded mine shafts fell on a continuum directly between local surface waters and those resulting from hydrothermal alteration suggesting an intermediate level of water-rock interaction in flooded mine shaft habitats. Concentrations of Li and B ranged from low micromolal in surface waters to millimolal in thermal waters. Other elements - Fe, Mn, Zn, and As included - were enriched in anoxic mine shafts by three to four orders of magnitude, due to exposure to and reaction with minerals. Concentrations of Fe and Zn ranged up to tens of millimolal whereas millimolal Mn and submillimolal As concentrations were reached. The transition from mostly unreacted surface water to waters nearly in equilibrium with rock provides vast geochemical habitat for microbes to exploit.

Evaluating remedial alternatives for an acid mine drainage stream: A model post audit

USGS Publications Warehouse

Runkel, Robert L.; Kimball, Briant A.; Walton-Day, Katherine; Verplanck, Philip L.; Broshears, Robert E.

2012-01-01

A post audit for a reactive transport model used to evaluate acid mine drainage treatment systems is presented herein. The post audit is based on a paired synoptic approach in which hydrogeochemical data are collected at low (existing conditions) and elevated (following treatment) pH. Data obtained under existing, low-pH conditions are used for calibration, and the resultant model is used to predict metal concentrations observed following treatment. Predictions for Al, As, Fe, H+, and Pb accurately reproduce the observed reduction in dissolved concentrations afforded by the treatment system, and the information provided in regard to standard attainment is also accurate (predictions correctly indicate attainment or nonattainment of water quality standards for 19 of 25 cases). Errors associated with Cd, Cu, and Zn are attributed to misspecification of sorbent mass (precipitated Fe). In addition to these specific results, the post audit provides insight in regard to calibration and sensitivity analysis that is contrary to conventional wisdom. Steps taken during the calibration process to improve simulations of As sorption were ultimately detrimental to the predictive results, for example, and the sensitivity analysis failed to bracket observed metal concentrations.

Investigating the Geochemical Model for Molybdenum Mineralization in the JEB Tailings Management Facility at McClean Lake, Saskatchewan: An X-ray Absorption Spectroscopy Study.

PubMed

Blanchard, Peter E R; Hayes, John R; Grosvenor, Andrew P; Rowson, John; Hughes, Kebbi; Brown, Caitlin

2015-06-02

The geochemical model for Mo mineralization in the JEB Tailings Management Facility (JEB TMF), operated by AREVA Resources Canada at McClean Lake, Saskatchewan, was investigated using X-ray Absorption Near-Edge Spectroscopy (XANES), an elemental-specific technique that is sensitive to low elemental concentrations. Twenty five samples collected during the 2013 sampling campaign from various locations and depths in the TMF were analyzed by XANES. Mo K-edge XANES analysis indicated that the tailings consisted primarily of Mo(6+) species: powellite (CaMoO4), ferrimolybdite (Fe2(MoO4)3·8H2O), and molybdate adsorbed on ferrihydrite (Fe(OH)3 - MoO4). A minor concentration of a Mo(4+) species in the form of molybdenite (MoS2) was also present. Changes in the Mo mineralization over time were inferred by comparing the relative amounts of the Mo species in the tailings to the independently measured aqueous Mo pore water concentration. It was found that ferrimolybdite and molybdate adsorbed on ferrihydrite initially dissolves in the TMF and precipitates as powellite.

Evaluating remedial alternatives for an acid mine drainage stream: a model post audit.

PubMed

Runkel, Robert L; Kimball, Briant A; Walton-Day, Katherine; Verplanck, Philip L; Broshears, Robert E

2012-01-03

A post audit for a reactive transport model used to evaluate acid mine drainage treatment systems is presented herein. The post audit is based on a paired synoptic approach in which hydrogeochemical data are collected at low (existing conditions) and elevated (following treatment) pH. Data obtained under existing, low-pH conditions are used for calibration, and the resultant model is used to predict metal concentrations observed following treatment. Predictions for Al, As, Fe, H(+), and Pb accurately reproduce the observed reduction in dissolved concentrations afforded by the treatment system, and the information provided in regard to standard attainment is also accurate (predictions correctly indicate attainment or nonattainment of water quality standards for 19 of 25 cases). Errors associated with Cd, Cu, and Zn are attributed to misspecification of sorbent mass (precipitated Fe). In addition to these specific results, the post audit provides insight in regard to calibration and sensitivity analysis that is contrary to conventional wisdom. Steps taken during the calibration process to improve simulations of As sorption were ultimately detrimental to the predictive results, for example, and the sensitivity analysis failed to bracket observed metal concentrations.

ROLE OF IRON AND MANGANESE OXIDES IN BIOSOLIDS AND BIOSOLIDS-AMENDED SOILS ON METAL BINDING

EPA Science Inventory

Biosolids contain high levels of Fe, Mn, and Al. Surfaces of freshly precipitated metal oxides, especially Fe and Mn, are known to be highly active sites for most dissolved metal ion species. We nw have metal sorption/desorption data that illustrate the importance of Fe and Mn fr...

Heterogeneous selenite reduction by zero valent iron steel wool.

PubMed

Li, Ziyan; Huang, Donglin; McDonald, Louis M

2017-02-01

Mine drainage from the low-sulfur surface coal mines in southern West Virginia, USA, is circumneutral (pH > 6) but contains elevated selenium (Se) concentrations. Removal of selenite ions from aqueous solutions under anoxic condition at pH 6-8.5 by zero valent iron steel wool (ZVI-SW) was investigated in bench-scale kinetic experiments using wet chemical, microscopic and spectroscopic techniques (X-ray photoelectron spectroscopy). ZVI-SW could effectively and efficiently remove Se IV from solution with pH 6-8.5. A two-step removal mechanism was identified for Se IV reduction by ZVI-SW. The proposed mechanism was electrochemical reduction of Se IV by Fe 0 in an initial lag stage, followed by a faster heterogeneous reduction, mediated by an Fe II -bearing phase (hydroxide or green rust). Solution pH was a critical factor for the kinetic rate in the lag stage (0.33 h -1 for pH > 8 and 0.10 h -1 for pH 6-8). The length of lag stage was 20-30 min as determined by the time for dissolved Fe II concentration to reach 0.30 ± 0.04 mg L -1 which was critical for induction of the faster stage. About 65% of the initial Se IV was reduced to Se 0 , the primary reductive product in both stages.

Photo-Fenton degradation of phenol, 2,4-dichlorophenoxyacetic acid and 2,4-dichlorophenol mixture in saline solution using a falling-film solar reactor.

PubMed

Luna, Airton J; Nascimento, Cláudio A O; Foletto, Edson Luiz; Moraes, José E F; Chiavone-Filhoe, Osvaldo

2014-01-01

In this work, a saline aqueous solution of phenol, 2,4-dichlorophenoxyacetic acid (2,4-D) and 2,4-dichlorophenol (2,4-DCP) was treated by the photo-Fenton process in a falling-film solar reactor. The influence of the parameters such as initial pH (5-7), initial concentration of Fe2+ (1-2.5mM) and rate of H202 addition (1.87-3.74mmol min-1) was investigated. The efficiency of photodegradation was determined from the removal of dissolved organic carbon (DOC), described by the species degradation of phenol, 2,4-D and 2,4-DCP. Response surface methodology was employed to assess the effects of the variables investigated, i.e. [Fe2+], [H202] and pH, in the photo-Fenton process with solar irradiation. The results reveal that the variables' initial concentration of Fe2+ and H202 presents predominant effect on pollutants' degradation in terms of DOC removal, while pH showed no influence. Under the most adequate experimental conditions, about 85% DOC removal was obtained in 180 min by using a reaction system employed here, and total removal of phenol, 2,4- and 2,4-DCP mixture in about 30min.

Significance of floods in metal dynamics and export in a small agricultural catchment

NASA Astrophysics Data System (ADS)

Roussiez, Vincent; Probst, Anne; Probst, Jean-Luc

2013-08-01

High-resolution monitoring of water discharge and water sampling were performed between early October 2006 and late September 2007 in the Montoussé River, a permanent stream draining an experimental agricultural catchment in Gascogne region (SW France). Dissolved and particulate concentrations of major elements and trace metals (i.e. Al, Fe, Mn, As, Cd, Cr, Cu, Ni, Pb, Sc and Zn) were examined. Our results showed that contamination levels were deficient to moderate, as a result of sustainable agricultural practices. Regarding dynamics, metal partitioning between particulate and dissolved phases was altered during flood conditions: the particulate phase was diluted by coarser and less contaminated particles from river bottom and banks, whereas the liquid phase was rapidly enriched owing to desorption mechanisms. Soluble/reactive elements were washed-off from soils at the beginning of the rain episode. The contribution of the flood event of May 2007 (by far the most significant episode over the study period) to the annual metal export was considerable for particulate forms (72-82%) and moderate for dissolved elements (0-20%). The hydrological functioning of the Montoussé stream poses dual threat on ecosystems, the consequences of which differ from both temporal and spatial scales: (i) desorption processes at the beginning of floods induce locally a rapid enrichment (up to 3.4-fold the pre-flood signatures on average for the event of May 2007) of waters in bioavailable metals, and (ii) labile metals - enriched by anthropogenic sources - associated to particles (mainly via carbonates and Fe/Mn oxides), were predominantly transferred during floods into downstream-connected rivers.